A solid-state probe for SO2/SO3 based on Na2SO4 I electrolyte

Conductivity measurements as a function of temperature and partial pressures of SOs, SO2, and O2, and transference experiments indicate that the transport number of Na + ions is unity in Na2SO4-I. A concentration cell based on this electrolyte Pt, O2' + SO2' + SOs'/Na2SO4-I/SOa" + SO~" + O~", Pt produces emf's that are in agreement with those calculated from the Nernst equation when equilibrium is assumed between the gas species at the electrodes. The cell can be used for monitoring the SO#SOs pollution in air, and in combination with an oxygen probe can be used for the determination of SO=/SOs concentrations in coal combustion reactors, for the evaluation of the partial pressure of $2 in coal gasification systems, and for emission control in nonferrous smelters using sulfide ores. The probe is similar to that developed recently by Gauthier et aL (4, 5) using K=SO4 as the electrolyte, but can operate at higher pressures of SO3. Because of the greater polarizing power of the Na+ ion compared to the K + ion, Na2S207 is less stable and can be formed only at a considerably higher pressure of S03 than that required for K~20~.

Some recent developments in solid state galvanic sensors

A critical revi<:w of the possibilities of measuring the ~artlal pressure of sulfur using solid state galvanic cells )'n;;cd on AgI, C" , B-alumina, CaO-Zr02' Na2S04-I and doped ;:":;, ,,,Ilil "Iltl ,,11: auxiliary "jectrodes are presentlOu. SOIll..., df tllc!iL' sYHtcmH h,}vu inherent limltntlol1$ when <:xl'o" ...d to environments contilining both oxygen and sulfur. Electrode polarization due to electronic conduction in the solid electrolyte is a significant factor limiting the ;lC'e,"'acy of isotlwrm:l1 cell",. The electrochemical flux of{lit' !'\)ndlwl Ill}: Ion LhnHO',h tht' ('!('ctrojyt(~ C:Ul },(,! llIinlnliz(,{j pfUjJL!f cell. dL:~) i.t',11. Noni!:iot.herm~ll cells \.Jlth temperaLure compensated reference electrodes have a number of advantages over thC'ir isothermal counterparts.

Solid state electrochemical sensor for monitoring Mg in Al refining process

Novel solid-state electrochemical sensors have been designed using the Mg2+ cation conductors incorporating novel solid-state reference electrodes for in-line monitoring of Mg in molten Al during the refining process and also for in-line monitoring of Mg content in molten Al in the alloying process. In this paper we report the preparation of Mg2+ ion conductors, MgAl2O4 and MgZr4(PO4)6, by the solid state ceramic synthesis route, measurement of their electrical properties using ac-impedance spectroscopy and application of the above cation conductors for designing novel electrochemical sensors for monitoring Mg dissolved in molten Al. The activation energy for Mg2+ ion conduction in MgAl2O4 is 2.08 eV and in MgZr4(PO4)6 is 1.7 eV, respectively. The sensors have been found to respond rapidly to change in Mg content in molten aluminium around 1000 K.

Combining adiabatic and Hartmann-Hahn cross-polarization for sensitivity enhancement in solid state separated local field 2D-NMR experiments of partially ordered systems

In this Letter, we examine magnetization in double- and zero-quantum reservoirs of an ensemble of spin-1/2 nuclei and describe their role in determining the sensitivity of a class of separated local field NMR experiments based on Hartmann-Hahn cross-polarization. We observe that for the liquid crystal system studied, a large dilute spin-polarization, obtained initially by the use of adiabatic cross-polarization, can enhance the sensitivity of the above experiment. The signal enhancement factors, however, are found to vary and depend on the local dynamics. The experimental results have been utilized to obtain the local order-parameters of the system. (C) 2012 Elsevier B. V. All rights reserved.

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.

A new 3D cadmium(II) coordination polymer having mu(4)-oxalato, mu-aquo and mu-chlorido bridges: crystal structure, solid state fluorescence and thermal behavior

A new 3D cadmium(II) coordination polymer, Cd(C2O4)(0.5)Cl(H2O)](n) (1) has been synthesized from a mixture of CdCl2. H2O and (NH4)(2)C2O4 in a slightly acidic pH. Its molecular structure was determined by single crystal X-ray diffraction which reveals that the new polymeric structure consists of simultaneous mu(4)-oxalato, mu-aquo, and mu-chlorido bridges between the metal centers, embedded in distorted pentagonal bipyramidal geometries. On thermal analysis compound exhibits high thermal stability up to 330 degrees C. Compound 1 also exhibits strong fluorescent emission. (c) 2013 Elsevier B.V. All rights reserved.

Morphology and electrochemical performance of graphene nanosheet array for Li-ion thin film battery

Highly branched and porous graphene nanosheet synthesized over different substrates as anode for Lithium ion thin film battery. These films synthesized by microwave plasma enhanced chemical vapor deposition at temperature 700 degrees C. Scanning electron microscopy and X-ray photo electron spectroscopy are used to characterize the film surface. It is found that the graphene sheets possess a curled and flower like morphology. Electrochemical performances were evaluated in swezelock type cells versus metallic lithium. A reversible capacity of 520 mAh/g, 450 mAh/g and 637 mAh/g was obtained after 50 cycles when current rate at 23 mu A cm(2) for CuGNS, NiGNS and PtGNS electrodes, respectively. Electrochemical properties of thin film anode were measured at different current rate and gave better cycle life and rate capability. These results indicate that the prepared high quality graphene sheets possess excellent electrochemical performances for lithium storage. (C) 2013 Elsevier Ltd. All rights reserved.

Computationally Efficient and Accurate Modeling of Li-ion Battery

A computationally efficient Li-ion battery model has been proposed in this paper. The battery model utilizes the features of both analytical and electrical circuit modeling techniques. The model is simple as it does not involve a look-up table technique and fast as it does not include a polynomial function during computation. The internal voltage of the battery is modeled as a linear function of the state-of-charge of the battery. The internal resistance is experimentally determined and the optimal value of resistance is considered for modeling. Experimental and simulated data are compared to validate the accuracy of the model.

Symbiosis in Solid State Interconversion and Synthon Modularity in Hydroxybenzoic Acid-Hexamine Adducts

Systematic cocrystallization of hydroxybenzoic acids with hexamine using liquid-assisted grinding shows facile solid state interconversion among different stoichiometric variants. The reversible interconversion caused by varying both the acid and base components in tandem is shown to be a consequence of hydrogen-bonded synthon modularity present in all representative crystal structures. Among a total of 11 complexes, three are salts and eight are cocrystals. The insulated synthons appear as conserved tetrameric motifs in the structures, and the mechanism of interconversion is closely monitored by the synthon modularity. The interconversion is consistent with the theoretically computed stabilization energies of all the tetramers found in this series of cocrystals based on atoms in molecule calculations.

Biomimetic molecular organization of naphthalene diimide in the solid state: tunable (chiro-) optical, viscoelastic and nanoscale properties

The interfacing of aromatic molecules with biomolecules to design functional molecular materials is a promising area of research. Intermolecular interactions determine the performance of these materials and therefore, precise control over the molecular organization is necessary to improve functional properties. Herein we describe the tunable biomimetic molecular engineering of a promising n-type organic semiconductor, naphthalene diimide (NDI), in the solid state by introducing minute structural mutations in the form of amino acids with variable Ca-functionality. For the first time we could achieve all four possible crystal packing modes, namely cofacial, brickwork, herringbone and slipped stacks of the NDI system. Furthermore, amino acid conjugated NDIs exhibit ultrasonication induced organogels with tunable visco-elastic and temperature responsive emission properties. The amino acid-NDI conjugates self-assemble into 0D nanospheres and 1D nanofibers in their gel state while the ethylamine-NDI conjugate forms 2D sheets from its solution. Photophysical studies indicated the remarkable influence of molecular ordering on the absorption and fluorescence properties of NDIs. Interestingly, the circular dichroism (CD) and X-ray diffraction (XRD) studies revealed the existence of helical ordering of NDIs in both solution and solid state. The chiral amino acids and their conformations with respect to the central NDI core are found to influence the nature of the helical organization of NDIs. Consequently, the origin of the preferential handedness in the helical organization is attributed to transcription of chiral information from the amino acid to the NDI core. On account of these unique properties, the materials derived from NDI-conjugates might find a wide range of future interdisciplinary applications from materials to biomedicine.

Dense network of O-H ... O and C-H ... O interactions in the solid state structure of n-pentyl-2-chloro-2-deoxy-alpha-D-manno-sept 3-uloside

Single crystal X-ray structural analysis of a septanoside, namely, n-pentyl-2-chloro-2-deoxy sept-3-uloside (1) provides many finer details of the molecular structure, in addition to its preferred twist-chair conformation, namely, (TC3,4)-T-5,6 conformation. Structural analysis reveals a dense network of O-H...O, C-H...O and van der Waals interactions that stabilize interdigitized, planar bi-layer structure of the crystal lattice. (C) 2014 Elsevier Ltd. All rights reserved.

Fine-tuning solid-state luminescence in NPIs (1,8-naphthalimides): impact of the molecular environment and cumulative interactions

An investigation of a series of seven angular ``V'' shaped NPIs (1-7) is presented. The effect of substitution of these structurally similar NPIs on their photophysical properties in the solution-state and the solid-state is presented and discussed in light of experimental and computational findings. Compounds 1-7 show negligible to intensely strong emission yields in their solid-state depending on the nature of substituents appended to the oxoaryl moiety. The solution and solid-state properties of the compounds can be directly correlated with their structural rigidity, nature of substituents and intermolecular interactions. The versatile solid-state structures of the NPI siblings are deeply affected by the pendant substituents. All of the NPIs (1-7) show antiparallel dimeric pi-pi stacking interactions in their solid-state which can further extend in a parallel, alternate, orthogonal or lateral fashion depending on the steric and electronic nature of the C-4' substituents. Structural investigations including Hirshfeld surface analysis methods reveal that where strongly interacting systems show weak to moderate emission in their condensed states, weakly interacting systems show strong emission yields under the same conditions. The nature of packing and extended structures also affects the emission colors of the NPIs in their solid-states. Furthermore, DFT computational studies were utilized to understand the molecular and cumulative electronic behaviors of the NPIs. The comprehensive studies provide insight into the condensed-state luminescence of aggregationprone small molecules like NPIs and help to correlate the structure-property relationships.

Pressure induced manifold enhancement of Li-kinetics in FCC fullerene

The reduction of the diffusion energy barrier for Li in electrodes is one of the required criteria to achieve better performances in Li ion batteries. Using density functional theory based calculations, we report a pressure induced manifold enhancement of Li-kinetics in bulk FCC fullerene. Scanning of the potential energy surface reveals a diffusion path with a low energy barrier of 0.62 eV, which reduces further under the application of hydrostatic pressure. The pressure induced reduction in the diffusion barrier continues till a uniform volume strain of 17.7% is reached. Further enhancement of strain increases the barrier due to the repulsion caused by C-C bond formation between two neighbouring fullerenes. The decrease in the barrier is attributed to the combined effect of charge transfer triggered by the enhanced interaction of Li with the fullerene as well as the change in profile of the local potential, which becomes more attractive for Li. The lowering of the barrier leads to an enhancement of two orders of magnitude in Li diffusivity at room temperature making pressurized bulk fullerene a promising artificial solid electrolyte interface (SEI) for a faster rechargeable battery.

Solid state structure of p-bromo phenyl 4,5,7-tri-O-benzyl-beta-D-glycero-D-talo-septanoside and an analysis of non-covalent interactions

The solid state structure of a new seven-membered sugar oxepane derivative, namely, p-bromo phenyl 4,5,7-tri-O-benzyl-beta-D-glycero-D-talo-septanoside is discussed, as determined through single crystal X-ray structural determination and in relation to their conformational features. The molecule adopts twist-chair as the preferred conformation, with conformational descriptor (TC2,3)-T-0,1. The solid state packing of molecules is governed by a rich network of non-covalent bonding originating from O-H center dot center dot center dot O, C-H center dot center dot center dot pi, C-H center dot center dot center dot Br and aromatic pi center dot center dot center dot pi interactions that stabilize the packing of molecules in the crystal. (C) 2015 Elsevier Ltd. All rights reserved.