Hydrolysis of Ammonia Borane as a Hydrogen Source: Fundamental Issues and Potential Solutions Towards Implementation

In todays era of energy crisis and global warming, hydrogen has been projected as a sustainable alternative to depleting CO2-emitting fossil fuels. However, its deployment as an energy source is impeded by many issues, one of the most important being storage. Chemical hydrogen storage materials, in particular B?N compounds such as ammonia borane, with a potential storage capacity of 19.6 wt?% H2 and 0.145 kg?H?2?L-1, have been intensively studied from the standpoint of addressing the storage issues. Ammonia borane undergoes dehydrogenation through hydrolysis at room temperature in the presence of a catalyst, but its practical implementation is hindered by several problems affecting all of the chemical compounds in the reaction scheme, including ammonia borane, water, borate byproducts, and hydrogen. In this Minireview, we exhaustively survey the state of the art, discuss the fundamental problems, and, where applicable, propose solutions with the prospect of technological applications.

Ion Transport in Liquid Salt Solutions with Oxide Dispersions:``Soggy Sand'' Electrolytes

``Soggy sand'' electrolyte, which essentially consists of oxide dispersions in nonaqueous liquid salt solutions, comprises an important class of soft matter electrolytes. The ion transport mechanism of soggy sand electrolyte is complex. The configuration of particles in the liquid solution has been observed to depend in a nontrivial manner on various parameters related to the oxide (concentration, size, surface chemistry) and solvent (dielectric constant, viscosity) as well as time. The state of the particles in solution not only affects ionic conductivity but also effectively the mechanical and electrochemical properties of the solid liquid composite. Apart from comprehensive understanding of the underlying phenomena that govern ion transport, which will benefit design of better electrolytes, the problem has far-reaching implications in diverse fields such as catalysis, colloid chemistry, and biotechnology.

Oscillatory settling in wormlike-micelle solutions: bursts and a long time scale

We study the dynamics of a spherical steel ball falling freely through a solution of entangled wormlike-micelles. If the sphere diameter is larger than a threshold value, the settling velocity shows repeated short oscillatory bursts separated by long periods of relative quiescence. We propose a model incorporating the interplay of settling-induced flow, viscoelastic stress and, as in M. E. Cates, D. A. Head and A. Ajdari, Phys. Rev. E, 2002, 66, 025202(R) and A. Aradian and M. E. Cates, Phys. Rev. E, 2006, 73, 041508, a slow structural variable for which our experiments offer independent evidence.

Understanding Aqueous Dispersibility of Graphene Oxide and Reduced Graphene Oxide through pK(a) Measurements

The chemistry underlying the aqueous dispersibility of graphene oxide (GO) and reduced graphene oxide (r-GO) is a key consideration in the design of solution processing techniques for the preparation of processable graphene sheets. Here, we use zeta potential measurements, pH titrations, and infrared spectroscopy to establish the chemistry underlying the aqueous dispersibility of GO and r-GO sheets at different values of pH. We show that r-GO sheets have ionizable groups with a single pK value (8.0) while GO sheets have groups that are more acidic (pK = 4.3), in addition to groups with pK values of 6.6 and 9.0. Infrared spectroscopy has been used to follow the sequence of ionization events. In both GO and r-GO sheets, it is ionization of the carboxylic groups that is primarily responsible for the build up of charge, but on GO sheets, the presence of phenolic and hydroxyl groups in close proximity to the carboxylic groups lowers the pK(a) value by stabilizing the carboxylate anion, resulting in superior water dispersibility.

Synthesis and Electrochemical Characterization of LiNi0.8Co0.2O2 as Cathode Material for Aqueous Rechargeable Lithium Batteries

LiNi0.8Co0.2O2 cathode material for lithium ion batteries is synthesized by reaction under autogenic pressure at elevated temperature (RAPET) method. The simple synthesis procedure is time and energy saving, and thus is promising for commercial application. The structure and stability of the material have been characterized by means of XRD and TG-DTA. The electrochemical properties of the LiNi0.8Co0.2O2 cathode are investigated in 2 M Li2SO4 aqueous electrolyte and they are compared to that in an organic electrolyte. A battery cell consisting of LiNi0.8Co0.2O2 as cathode in 2 M Li2SO4 solution is constructed in combination with LiTi2 (PO4)(3) as anode. The cell retained almost constant discharge capacity over hundred cycles. The electrochemical impedance spectral ( EIS) studies in aqueous and nonaqueous electrolytes revealed that the mechanism of lithium ion intercalation and deintercalation processes in LiNi0.8Co0.2O2 electrode follow almost similar mechanism in both aqueous and nonaqueous electrolytes. The chemical diffusion coefficient was calculated from slow scan rate cyclic voltammetry and EIS. (C) 2012 The Electrochemical Society. DOI: 10.1149/2.075205jes] All rights reserved.

Hydration dynamics of protein molecules in aqueous solution: Unity among diversity

Dielectric dispersion and NMRD experiments have revealed that a significant fraction of water molecules in the hydration shell of various proteins do not exhibit any slowing down of dynamics. This is usually attributed to the presence of the hydrophobic residues (HBR) on the surface, although HBRs alone cannot account for the large amplitude of the fast component. Solvation dynamics experiments and also computer simulation studies, on the other hand, repeatedly observed the presence of a non-negligible slow component. Here we show, by considering three well-known proteins (lysozyme, myoglobin and adelynate kinase), that the fast component arises partly from the response of those water molecules that are hydrogen bonded with the backbone oxygen (BBO) atoms. These are structurally and energetically less stable than those with the side chain oxygen (SCO) atoms. In addition, the electrostatic interaction energy distribution (EIED) of individual water molecules (hydrogen bonded to SCO) with side chain oxygen atoms shows a surprising two peak character with the lower energy peak almost coincident with the energy distribution of water hydrogen bonded to backbone oxygen atoms (BBO). This two peak contribution appears to be quite general as we find it for lysozyme, myoglobin and adenylate kinase (ADK). The sharp peak of EIED at small energy (at less than 2 k(B)T) for the BBO atoms, together with the first peak of EIED of SCO and the HBRs on the protein surface, explain why a large fraction (similar to 80%) of water in the protein hydration layer remains almost as mobile as bulk water Significant slowness arises only from the hydrogen bonds that populate the second peak of EIED at larger energy (at about 4 k(B)T). Thus, if we consider hydrogen bond interaction alone, only 15-20% of water molecules in the protein hydration layer can exhibit slow dynamics, resulting in an average relaxation time of about 5-10 ps. The latter estimate assumes a time constant of 20-100 ps for the slow component. Interestingly, relaxation of water molecules hydrogen bonded to back bone oxygen exhibit an initial component faster than the bulk, suggesting that hydrogen bonding of these water molecules remains frustrated. This explanation of the heterogeneous and non-exponential dynamics of water in the hydration layer is quantitatively consistent with all the available experimental results, and provides unification among diverse features.

Wrinkled and slack membranes: nonlinear 3D elasticity solutions via smooth DMS-FEM and experiment

The smooth DMS-FEM, recently proposed by the authors, is extended and applied to the geometrically nonlinear and ill-posed problem of a deformed and wrinkled/slack membrane. A key feature of this work is that three-dimensional nonlinear elasticity equations corresponding to linear momentum balance, without any dimensional reduction and the associated approximations, directly serve as the membrane governing equations. Domain discretization is performed with triangular prism elements and the higher order (C1 or more) interelement continuity of the shape functions ensures that the errors arising from possible jumps in the first derivatives of the conventional C0 shape functions do not propagate because the ill-conditioned tangent stiffness matrices are iteratively inverted. The present scheme employs no regularization and exhibits little sensitivity to h-refinement. Although the numerically computed deformed membrane profiles do show some sensitivity to initial imperfections (nonplanarity) in the membrane profile needed to initiate transverse deformations, the overall patterns of the wrinkles and the deformed shapes appear to be less so. Finally, the deformed profiles, computed through the DMS FEM-based weak formulation, are compared with those obtained through an experiment on an ultrathin Kapton membrane, wherein wrinkles form because of the applied boundary displacement conditions. Comparisons with a reported experiment on a rectangular membrane are also provided. These exercises lend credence to the feasibility of the DMS FEM-based numerical route to computing post-wrinkled membrane shapes. Copyright (c) 2012 John Wiley & Sons, Ltd.

Uptake of permanganate from aqueous environment by surfactant modified montmorillonite batch and fixed bed studies

Organo-clay was prepared by incorporating different amounts (in terms of CEC, ranging from 134-840 mg of quaternary ammonium cation (QACs) such as hexadecytrimethylammonium bromide (C19H42N]Br) into the montmorillonite clay. Prepared organo-clays are characterized by CHN analyser and XRD to measure the amount of elemental content and interlayer spacing of surfactant modified clay. The batch experiments of sorption of permanganate from aqueous media by organo-clays was studied at different acidic strengths (pH 1-7). The experimental results show that the rate and amount of adsorption of permanganate was higher at lower pH compared to raw montmorillonite. Laboratory fixed bed experiments were conducted to evaluate the breakthrough time and nature of breakthrough curves. The shape of the breakthrough curves shows that the initial cationic surfactant loadings at 1.0 CEC of the clay is enough to enter the permanganate ions in to the interlamellar region of the surfactant modified smectile clays. These fixed bed studies were also applied to quantify the effect of bed-depth and breakthrough time during the uptake of permanganate. Calculation of thermodynamic parameters shows that the sorption of permanganate is spontaneous and follows the first order kinetics.

Iron(III) Chloride-Catalysed Aerobic Reduction of Olefins using Aqueous Hydrazine at Ambient Temperature

A chemoselective reduction of olefins and acetylenes is demonstrated by employing catalytic amounts of ferric chloride hexahydrate (FeCl3 center dot 6H(2)O) and aqueous hydrazine (NH2NH2 center dot H2O) as hydrogen source at room temperature. The reduction is chemoselective and tolerates a variety of reducible functional groups. Unlike other metal-catalysed reduction methods, the present method employs a minimum amount of aqueous hydrazine (1.5-2 equiv.). Also, the scope of this method is demonstrated in the synthesis of ibuprofen in aqueous medium.

Dilithium phthalocyanine as a catalyst for oxygen reduction in non-aqueous Li-O-2 cells

The electrochemical performance of Li-O-2 cells depends mainly on the kinetics of the cathode reaction, namely, oxygen reduction reaction in non-aqueous electrolytes. The catalyst plays an important role on the kinetics of the reaction. In the present work, dilithium phthalocyanine is used as the catalyst in the cathode of Li-O-2 cells. Dual-layer O-2 electrodes are fabricated employing a high surface area microporous carbon with Ni gauge current collector present between the two layers. Discharge capacity of Li-O-2 cell measured at 0.2 mA.cm(-2) is about 30 mAh.cm(-2). Phthalocyanine ring is considered to interact with O-2 producing Li2Pc+delta - O-2(-delta) as a reaction intermediate, which facilitates the electron-transfer reaction.

Guanidine catalyzed aerobic reduction: a selective aerobic hydrogenation of olefins using aqueous hydrazine

An efficient aerobic reduction of olefins, internal as well as terminal, is developed using guanidine as an organocatalyst. A remarkable chemoselectivity in reduction has been demonstrated in the presence of a variety of functional groups and protective groups and a selective reduction of a terminal olefin in the presence of an internal olefin is revealed.

The effect of potential on electrodeposited CdSe thin films

Cadmium selenide (CdSe) thin films have been successfully prepared by the electrodeposition technique on indium doped tin oxide (ITO) substrates with aqueous solutions of cadmium sulphate and selenium dioxide. The deposited films were characterized with X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive analysis by X-rays (EDAX), photoluminescence (PL), UV spectrometry and electrical resistivity measurements. XRD analysis shows that the films are polycrystalline in nature with hexagonal crystalline structure. The various parameters such as crystallite size, micro strain, dislocation density and texture coefficients were evaluated. SEM study shows that the total substrate surface is well covered with uniformly distributed spherical shaped grains. Photoluminescence spectra of films were recorded to understand the emission properties of the films. The presence of direct transition with band gap energy 1.75 eV is established from optical studies. The electrical resistivity of the thin films is found to be 10(6) Omega cm and the results are discussed. (c) 2011 Elsevier Ltd. All rights reserved.

Cyclodextrin functionalized magnetic iron oxide nanocrystals: a host-carrier for magnetic separation of non-polar molecules and arsenic from aqueous media

A single-step magnetic separation procedure that can remove both organic pollutants and arsenic from contaminated water is clearly a desirable goal. Here we show that water dispersible magnetite nanoparticles prepared by anchoring carboxymethyl-beta-cyclodextrin (CMCD) cavities to the surface of magnetic nanoparticles are suitable host carriers for such a process. Monodisperse, 10 nm, spherical magnetite, Fe3O4, nanocrystals were prepared by the thermal decomposition of FeOOH. Trace amounts of antiferromagnet, FeO, present in the particles provides an exchange bias field that results in a high superparamagnetic blocking temperature and appreciable magnetization values that facilitate easy separation of the nanocrystals from aqueous dispersions on application of modest magnetic fields. We show here that small molecules like naphthalene and naphthol can be removed from aqueous media by forming inclusion complexes with the anchored cavities of the CMCD-Fe3O4 nanocrystals followed by separation of the nanocrystals by application of a magnetic field. The adsorption properties of the iron oxide surface towards As ions are unaffected by the CMCD capping so it too can be simultaneously removed in the separation process. The CMCD-Fe3O4 nanocrystals provide a versatile platform for magnetic separation with potential applications in water remediation.

Effect of doping concentration on the structural and optical properties of pure and tin doped zinc oxide thin films by nebulizer spray pyrolysis (NSP) technique

Pure and tin doped zinc oxide (Sn:ZnO) thin films were prepared for the first time by NSP technique using aqueous solutions of zinc acetate dehydrate, tin (IV) chloride fendahydrate and methanol. X-ray diffraction patterns confirm that the films are polycrystalline in nature exhibiting hexagonal wurtzite type, with (0 0 2) as preferred orientation. The structural parameters such as lattice constant ('a' and `c'), crystallite size, dislocation density, micro strain, stress and texture coefficient were calculated from X-ray diffraction studies. Surface morphology was found to be modified with increasing Sn doping concentration. The ZnO films have high transmittance 85% in the visible region, and the transmittance is found to be decreased with the increase of Sn doping concentration. The corresponding optical band gap decreases from 3.25 to 3.08 eV. Room temperature photoluminescence reveals the sharp emission of strong UV peak at 400 nm (3.10 eV) and a strong sharp green luminescence at 528 nm (2.34 eV) in the Sn doped ZnO films. The electrical resistivity is found to be 10(6) Omega-cm at higher temperature and 10(5) Omega-cm at lower temperature. (C) 2012 Elsevier Ltd. All rights reserved.