One step synthesis of monoclinic VO2 (B) bundles of nanorods: Cathode for Li ion battery

One of the metastable phases of vanadium dioxide, VO2(B) bundles of nanorods and microspheres have been synthesized through a simple hydrothermal method by dispersing V2O5 in aqueous quinol. The obtained products were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and electrochemical discharge-charge test for lithium battery. It was found that the morphologies of the obtained VO2(B) can be tuned by manipulating the relative amount of quinol. The electrochemical test found that the bundles of nanorods exhibit an initial discharge capacity of 171 mAh g(-1) and its almost stabilized capacity was reached to 108 mAh g(-1) after 47 cycles at a current density of 0.1 mA g(-1). The formation mechanism of the VO2(B) bundles of nanorods and microspheres was also discussed. (C) 2012 Elsevier Inc. All rights reserved.

Hydrothermal synthesis of a monoclinic VO2 nanotube-graphene hybrid for use as cathode material in lithium ion batteries

The hydrothermal reaction of a mixture of a colloidal dispersion of graphite oxide and ammonium vanadate yielded a hybrid made of graphene and a nanotubular metastable monoclinic polymorph of VO2, known as VO2(B). The formation of VO2(B) nanotubes is accompanied by the reduction of graphite oxide. Initially the partially scrolled graphite oxide layers act as templates for the crystallization of VO2(B) in the tubular morphology. This is followed by the reduction of graphite oxide to graphene resulting in a hybrid in which VO2(B) nanotubes are dispersed in graphene. Electron microscopic studies of the hybrid reveal that the VO2(B) nanotubes are wrapped by and trapped between graphene sheets. The hybrid shows potential to be a high capacity cathode material for lithium ion batteries. It exhibits a high capacity (similar to 450 mAh/g) and cycling stability. The high capacity of the hybrid is attributed to the interaction between the graphene sheets and the VO2(B) tubes which improves the charge-transfer. The graphene matrix prevents the aggregation of the VO2(B) nanotubes leading to high cycling stability. (C) 2012 Elsevier Ltd. All rights reserved.

Benefits of Electronic Wiring and Spacers on Lithium Storage in Nanostructured Lithium-Ion Battery Anodes

The demand for high power density lithium-ion batteries (LIBs) for diverse applications ranging from mobile electronics to electric vehicles have resulted in an upsurge in the development of nanostructured electrode materials worldwide. Graphite has been the anode of choice in commercial LiBs. Due to several detrimental electrochemical and environmental issues, efforts are now on to develop alternative non-carbonaceous anodes which are safe, nontoxic and cost effective and at the same time exhibit high lithium storage capacity and rate capability. Titania (TiO2) and tin (Sn) based systems have gained much attention as alternative anode materials. Nanostructuring of TiO2 and SnO2 have resulted in enhancement of structural stability and electrochemical performances. Additionally, electronic wiring of mesoporous materials using carbon also effectively enhanced electronic conductivity of mesoporous electrode materials. We discuss in this article the beneficial influence of structural spacers and electronic wiring in anatase titania (TiO2) and tin dioxide (SnO2).

A broad pore size distribution mesoporous SnO2 as anode for lithium-ion batteries

We demonstrate here that mesoporous tin dioxide (abbreviated M-SnO2) with a broad pore size distribution can be a prospective anode in lithium-ion batteries. M-SnO2 with pore size ranging between 2 and 7.5 nm was synthesized using a hydrothermal procedure involving two different surfactants of slightly different sizes, and characterized. The irreversible capacity loss that occurs during the first discharge and charge cycle is 890 mAh g(-1), which is smaller than the 1,010-mAh g(-1) loss recorded for mesoporous SnO2 (abbreviated S-SnO2) synthesized using a single surfactant. After 50 cycles, the discharge capacity of M-SnO2 (504 mAh g(-1)) is higher than that of S-SnO2 (401 mAh g(-1)) and solid nanoparticles of SnO2 (abbreviated nano-SnO2 < 4 mAh g(-1)) and nano-SnO2. Transmission electron microscopy revealed higher disorder in the pore arrangement in M-SnO2. This, in turn imparts lower stiffness to M-SnO2 (elastic modulus, E (R) a parts per thousand aEuro parts per thousand 14.5 GPa) vis-a-vis S-SnO2 (E (R) a parts per thousand aEuro parts per thousand 20.5 GPa), as obtained using the nanoindentation technique. Thus, the superior battery performance of M-SnO2 is attributed to its intrinsic material mechanical property. The fluidity of the internal microstructure of M-SnO2 resulted in a lower degree of aggregation of Sn particles compared to S-SnO2 and nano-SnO2 structural stabilization and long-term cyclability.

A phenanthrene based highly selective fluorogenic and visual sensor for Cu2+ ion with nanomolar detection limit and its application in live cell imaging

A new phenanthrene based chemosensor has been synthesized and investigated to act as highly selective fluorescence and visual sensor for Cu2+ ion with very low detection limit of 1.58 nM: this has also been used to image Cu2+ in human cervical HeLa cancer cells. (C) 2012 Elsevier B.V. All rights reserved.

Metal and Alloy Nanoparticles by Amine-Borane Reduction of Metal Salts by Solid-Phase Synthesis: Atom Economy and Green Process

A new solid state synthetic route has been developed toward metal and bimetallic alloy nanoparticles from metal salts employing amine-boranes, as the reducing agent. During the reduction, amine-borane plays a dual role: acts as a reducing agent and reduces the metal salts to their elemental form and simultaneously generates a stabilizing agent in situ which controls the growth of the particles and stabilizes them in the nanosize regime. Employing different amine-boranes with differing reducing ability (ammonia borane (AB), dimethylamine borane (DMAB), and triethylamine borane (TMAB)) was found to have a profound effect on the particle size and the size distribution. Usage of AB as the reducing agent provided the smallest possible size with best size distribution. Employment of TMAB also afforded similar results; however, when DMAB was used as the reducing agent it resulted in larger sized nanoparticles that are polydisperse too. In the AB mediated reduction, BNHx polymer generated in situ acts as a capping agent whereas, the complexing amine of the other amine-boranes (DMAB and TMAB) play the same role. Employing the solid state route described herein, monometallic Au, Ag, Cu, Pd, and Ir and bimetallic CuAg and CuAu alloy nanoparticles of <10 nm were successfully prepared. Nucleation and growth processes that control the size and the size distribution of the resulting nanoparticles have been elucidated in these systems.

Generalized top-spin analysis and new physics in e(+)e(-) collisions with beam polarization

A generalized top-spin analysis proposed some time ago in the context of the standard model and subsequently studied in varying contexts is now applied primarily to the case of e(+)e(-) -> t (tww) over bar with transversely polarized beams. This extends our recent work with new physics couplings of scalar (S) and tensor (T) types. We carry out a comprehensive analysis assuming only the electron beam to be transversely polarized, which is sufficient to probe these interactions, and also eliminates any azimuthal angular dependence due to the standard model or new physics of the vector (V) and axial-vector (A) type interactions. We then consider new physics of the general four-Fermi type of V and A type with both beams transversely polarized and discuss implications with longitudinal polarization as well. The generalized spin bases are all investigated in the presence of either longitudinal or transverse beam polarization to look for appreciable deviation from the SM prediction in case of the new physics. 90% confidence level limits are obtained on the interactions for the generalized spin bases with realistic integrated luminosity. In order to achieve this we present a general discussion based on helicity amplitudes and derive a general transformation matrix that enables us to treat the spin basis. We find that beamline basis combined with transverse polarization provides an excellent window of opportunity both for S, T and V, A new physics, followed by the off-diagonal basis. The helicity basis is shown to be the best in case of longitudinal polarization to look for new physics effects due to V and A. DOI: 10.1103/PhysRevD.86.114019

Metal-Ion Metathesis in Metal-Organic Frameworks: A Synthetic Route to New Metal-Organic Frameworks

A porous metalorganic framework, Mn(H3O)(Mn4Cl)(3)(hmtt)(8)] (POST-65), was prepared by the reaction of 5,5',10,10',15,15'-hexamethyltruxene-2,7,12-tricarboxylic acid (H(3)hmtt) with MnCl2 under solvothermal conditions. POST-65(Mn) was subjected to post-synthetic modification with Fe, Co, Ni, and Cu according to an ion-exchange method that resulted in the formation of three isomorphous frameworks, POST-65(Co/Ni/Cu), as well as a new framework, POST-65(Fe). The ion-exchanged samples could not be prepared by regular solvothermal reactions. The complete exchange of the metal ions and retention of the framework structure were verified by inductively coupled plasmaatomic emission spectrometry (ICP-AES), powder X-ray diffraction (PXRD), and BrunauerEmmettTeller (BET) surface-area analysis. Single-crystal X-ray diffractions studies revealed a single-crystal-to-single-crystal (SCSC)-transformation nature of the ion-exchange process. Hydrogen-sorption and magnetization measurements showed metal-specific properties of POST-65.

Top-spin analysis of new scalar and tensor interactions in e(+) e (-) collisions with transverse beam polarization

The top polarization at the International Linear Collider (ILC) with transverse beam polarization is utilized in the process to probe interactions of the scalar and tensor type beyond the Standard Model and to disentangle their individual contributions. Confidence level limits of 90% are presented on the interactions with realistic integrated luminosity and are found to improve by an order of magnitude compared to the case when the spin of the top quark is not measured. Sensitivities of the order of a few times 10 (-aEuro parts per thousand 3) TeV (-aEuro parts per thousand 2) for real and imaginary parts of both scalar and tensor couplings at and 800 GeV with an integrated luminosity of 500 fb (-aEuro parts per thousand 1) and completely polarized beams are shown to be possible.

High precision Mg isotope measurements of meteoritic samples by secondary ion mass spectrometry

The possibility of establishing an accurate relative chronology of the early solar system events based on the decay of short-lived Al-26 to Mg-26 (half-life of 0.72 Myr) depends on the level of homogeneity (or heterogeneity) of Al-26 and Mg isotopes. However, this level is difficult. to constrain precisely because of the very high precision needed for the determination of isotopic ratios, typically of +/- 5 ppm. In this study, we report for the first time a detailed analytical protocol developed for high precision in situ Mg isotopic measurements ((25)mg/(24)mg and (26)mg/Mg-24 ratios, as well as Mg-26 excess) by MC-SIMS. As the data reduction process is critical for both accuracy and precision of the final isotopic results, factors such as the Faraday cup (FC) background drift and matrix effects on instrumental fractionation have been investigated. Indeed these instrumental effects impacting the measured Mg-isotope ratios can be as large or larger than the variations we are looking for to constrain the initial distribution of Al-26 and Mg isotopes in the early solar system. Our results show that they definitely are limiting factors regarding the precision of Mg isotopic compositions, and that an under- or over-correction of both FC background instabilities and instrumental isotopic fractionation leads to important bias on delta Mg-25, delta(26)mg and Delta Mg-26 values (for example, olivines not corrected for FC background drifts display Delta Mg-26 values that can differ by as much as 10 ppm from the truly corrected value). The new data reduction process described here can then be applied to meteoritic samples (components of chondritic meteorites for instance) to accurately establish their relative chronology of formation.

Ultrafast photoinduced enhancement of nonlinear optical response in 15-atom gold clusters on indium tin oxide conducting film

We show that the third order optical nonlinearity of 15-atom gold clusters is significantly enhanced when in contact with indium tin oxide (ITO) conducting film. Open and close aperture z-scan experiments together with non-degenerate pump-probe differential transmission experiments were done using 80 fs laser pulses centered at 395 nm and 790 nm on gold clusters encased inside cyclodextrin cavities. We show that two photon absorption coefficient is enhanced by an order of magnitude as compared to that when the clusters are on pristine glass plate. The enhancement for the nonlinear optical refraction coefficient is similar to 3 times. The photo-induced excited state absorption using pump-probe experiments at pump wavelength of 395 nm and probe at 790 nm also show an enhancement by an order of magnitude. These results attributed to the excited state energy transfer in the coupled gold cluster-ITO system are different from the enhancement seen so far in charge donor-acceptor complexes and nanoparticle-conjugate polymer composites.

A new approach for understanding ion transport in glasses; example of complex alkali diborate glasses containing lead, bismuth and tellurium oxides

Mechanism of ion transport in glasses continues to be incompletely understood. Several of the theoretical models in vogue fail to rationalize conductivity behaviour when d.c. and a.c. measurements are considered together. While they seem to involve the presence of at least two components in d.c. activation energy, experiments fail to reveal that feature. Further, only minor importance is given to the influence of structure of the glass on the ionic conductivity behaviour. In this paper, we have examined several general aspects of ion transport taking the example of ionically conducting glasses in pseudo binary, yNa(2)B(4)O(7)center dot(1-y) M (a) O (b) (with y = 0 center dot 25-0 center dot 79 and M (a) O (b) = PbO, TeO2 and Bi2O3) system of glasses which have also been recently characterized. Ion transport in them has been studied in detail. We have proposed that non-bridging oxygen (NBO) participation is crucial to the understanding of the observed conductivity behaviour. NBO-BO switching is projected as the first important step in ion transport and alkali ion jump is a subsequent event with a characteristically lower barrier which is, therefore, not observed in any study. All important observations in d.c. and a.c. transport in glasses are found consistent with this model.

Ion transport studies in lithium phospho-molybdate glasses containing Cl- ion

Ion conducting glasses in xLiCl-20Li(2)O-(80-x) 0.80P(2)O(5)-0.20MoO(3)] glass system have been prepared over a wide range of composition (X = 5, 10, 15, 20 and 25 mol%). The electrical conductivity and dielectric relaxation of these glasses were analyzed using impedance spectroscopy in the frequency range of 10 Hz-10 MHz and in the temperature range of 313-353 K. D.c. activation energies extracted from Arrhenius plots using regression analysis, decreases with increasing LiCl mol%. A.c. conductivity data has been fitted to both single and double power law equation with both fixed and variable parameters. The increased conductivity in the present glass system has been correlated with the volume increasing effect and the coordination changes that occur due to structural modification resulting in the creation of non-bridging oxygens (NBO's) of the type O-Mo-O- bonds in the glass network. Dielectric relaxation mechanism in these glasses is analyzed using Kohlrausch-Williams-Watts (KWW) stretched exponential function and stretched exponent (beta) is found to be insensitive to temperature.

Ellagic acid - a novel organic electrode material for high capacity lithium ion batteries

Ellagic acid, a naturally occurring polyphenol, extracted from pomegranate husk, is found to be a very good organic electrode material for rechargeable lithium batteries with high reversible capacities of similar to 450 and 200 mA h g(-1) at C/10 and C/2.5 discharge rates, respectively; ex situ NMR studies reveal possible lithiation-delithiation modes at different stages of the charge-discharge process.

A multi-sheeted three-dimensional potential-energy surface for the H-atom photodissociation of phenol

Extending the previous work of Lan et al. J. Chem. Phys., 122, 224315 (2005)], a multi-state potential model for the H atom photodissociation is presented. All three ``disappearing coordinates'' of the departing H atom have been considered. Ab initio CASSCF computations have been carried out for the linear COH geometry of C-2v symmetry, and for several COH angles with the OH group in the ring plane and also perpendicular to the ring plane. By keeping the C6H5O fragment frozen in a C-2v-constrained geometry throughout, we have been able to apply symmetry-based simplifications in the constructions of a diabatic model. This model is able to capture the overall trends of twelve adiabats at both torsional limits for a wide range of COH bend angles.