Hydrogen generation fromammonia borane using nanocatalysts

The rapidly depleting petroleum feed stocks and increasing green house gas emissions around the world has necessitated a search for alternative renewable energy sources. Hydrogen with molecular weight of 2.016 g/mol and high chemical energy per mass equal to 142 MJ/kg has clearly emerged as an alternative to hydrocarbon fuels. Means for safe and cost effective storage are needed for widespread usage of hydrogen as a fuel.Chemical storage is the one of the safer ways to store hydrogen compared to compressed and liquefied hydrogen. It involves storing hydrogen in chemical bonds in molecules and materials where an on-board reaction is used to release hydrogen. Ammonia–borane, (AB,H3N·BH3) with a potential capacity of 19.6 wt% is considered a very promising solid state hydrogen storage material. It is thermally stable at ambient temperatures. There are two major routes for the generation of H2 from AB: catalytic hydrolysis/alcoholysis and catalytic thermal decomposition. There has been a flurry of research activity on the generation of H2 from AB recently. The present review deals with an overview of our efforts in developing cost-effective nanocatalysts for hydrogen generation from ammonia borane in protic solvents.

Studies on hydrogen-bonds .4. proposed working criteria for assessing qualitative strength of hydrogen-bonds

The data obtained in the earlier parts of this series for the donor and acceptor end parameters of N-H. O and O-H. O hydrogen bonds have been utilised to obtain a qualitative working criterion to classify the hydrogen bonds into three categories: “very good” (VG), “moderately good” (MG) and weak (W). The general distribution curves for all the four parameters are found to be nearly of the Gaussian type. Assuming that the VG hydrogen bonds lie between 0 and ± la, MG hydrogen bonds between ± 1s̀ and ± 2s̀, W hydrogen bonds beyond ± 2s̀ (where s̀ is the standard deviation), suitable cut-off limits for classifying the hydrogen bonds in the three categories have been derived. These limits are used to get VG and MG ranges for the four parameters 1 and θ (at the donor end) and ± and ± (at the acceptor end). The qualitative strength of a hydrogen bond is decided by the cumulative application of the criteria to all the four parameters. The criterion has been further applied to some practical examples in conformational studies such as α-helix and can be used for obtaining suitable location of hydrogen atoms to form good hydrogen bonds. An empirical approach to the energy of hydrogen bonds in the three categories has also been presented.

Creep behaviour of Fe3Al-based alloys in DO3 phase field

A study is made to bring out the effect of alloying with Cr, Ti or Mn on the creep behaviour of Fe3Al. Impression creep experiments have been carried out in the DO3 phase field. In all the alloys, power law creep behaviour is observed in the stress range covered. The stress exponent for steady state creep rate and the activation energy for creep indicate that the creep rate is controlled by the dislocation climb process. Among the alloying elements studied, addition of Ti is most effective in improving the creep resistance.

Nanostructured titanium-nickel alloys: a comparison of processing routes

Rapid solidification, mechanical alloying and devitrificaiton of precursor metallic glasses are all possible routes for the synthesis of nanocrystals and nanocomposites, though their efficacy is system dependent. In a comprehensive study of alloys across the Ti-Ni phase diagram, nanocrystals of Ti and Ni and nanocomposites of alpha -Ti and Ti sub 2 Ni, Ti sub 2 Ni and TiNi and beta -Ti and glass have been produced. By the addition of Al, devitrification of metallic glasses created by mechanical alloying led to nanocrystalline intermetallic compounds. The evolution of these nanocrystalline microstructures has been rationalized on the basis of thermodynamic and kinetic considerations involving the metastable phase diagram for this system.

Analysis of oxide and vanadate supports for catalytic hydrogen combustion: Kinetic and mechanistic investigations

Combustion synthesized oxide and vanadate compounds (CeO2, Fe2O3, CeVO4, and FeVO4) were tested for catalytic hydrogen combustion. The compounds were characterized by X-ray diffraction and X-ray photoelectron spectroscopy. All the four compounds showed good activity and stability for catalytic hydrogen combustion and more than 95% conversion was observed over all the compounds within 500 degrees C. The mechanisms for the reaction over the different classes of compounds (cerium-based and iron-based compounds) were proposed on the basis of spectroscopic observations. The main difference in the mechanisms was in the nature of adsorption of H2 over the sites. The elementary processes for the reaction were proposed, corresponding rate expressions were derived, and the rate parameters for the reaction were estimated using nonlinear regression. Langmuir-Hinshelwood and Eley-Rideal mechanisms were also tested for the reaction and the proposed mechanism was compared with these mechanisms. (c) 2011 American Institute of Chemical Engineers AIChE J, 2012

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.

Asparagine and glutamine differ in their propensities to form specific side chain-backbone hydrogen bonded motifs in proteins

Short range side chain-backbone hydrogen bonded motifs involving Asn and Gln residues have been identified from a data set of 1370 protein crystal structures (resolution = 1.5 angstrom). Hydrogen bonds involving residues i - 5 to i + 5 have been considered. Out of 12,901 Asn residues, 3403 residues (26.4%) participate in such interactions, while out of 10,934 Gln residues, 1780 Gln residues (16.3%) are involved in these motifs. Hydrogen bonded ring sizes (Cn, where n is the number of atoms involved), directionality and internal torsion angles are used to classify motifs. The occurrence of the various motifs in the contexts of protein structure is illustrated. Distinct differences are established between the nature of motifs formed by Asn and Gln residues. For Asn, the most highly populated motifs are the C10 (COdi .NHi + 2), C13 (COdi .NHi + 3) and C17 (NdHi .COi - 4) structures. In contrast, Gln predominantly forms C16 (COei .NHi - 3), C12 (NeHi .COi - 2), C15 (NeHi .COi - 3) and C18 (NeHi .COi - 4) motifs, with only the C18motif being analogous to the Asn C17structure. Specific conformational types are established for the Asn containing motifs, which mimic backbone beta-turns and a-turns. Histidine residues are shown to serve as a mimic for Asn residues in side chain-backbone hydrogen bonded ring motifs. Illustrative examples from protein structures are considered. Proteins 2012; (c) 2011 Wiley Periodicals, Inc.

Intra-molecular hydrogen bonding with organic fluorine in the solution state: Deriving evidence by a two dimensional NMR experiment

The direct evidence for the existence of intra-molecular C-F center dot center dot center dot H-N hydrogen bond in organofluorine molecules, in the liquid state, is derived using NMR spectroscopy by the detection of long range interactions among fluorine, nitrogen and hydrogen atoms. The present study reports the determination of the relative signs and magnitudes of through space and through bond couplings to draw unambiguous evidence on the existence of weak molecular interactions involving organic fluorine. It is a simple, easy to implement, N-15 natural abundant two dimensional heteronuclear N-15-H-1 double quantum-single quantum correlation experiment. The existence of intra-molecular hydrogen bond is conclusively established in the investigated molecules. (C) 2011 Elsevier B.V. All rights reserved.

Accumulative roll bonding of aluminum alloys 2219/5086 laminates: Microstructural evolution and tensile properties

The present study describes the course of microstructure evolution during accumulative roll bonding (ARB) of dissimilar aluminum alloys AA2219 and AA5086. The two alloys were sandwiched as alternate layers and rolled at 300 degrees C up to 8 passes with 50% height reduction per pass. A strong bonding between successive layers accompanied by substantial grain refinement (similar to 200-300 nm) is achieved after 8 passes of ARB. The processing schedule has successfully maintained the iso-strain condition up to 6 cycles between the two alloys. Afterwards, the fracture and fragmentation of AA5086 layers dominate the microstructure evolution. Mechanical properties of the 8 pass ARB processed material were evaluated in comparison to the two starting alloy sheets via room temperature tensile tests along the rolling direction. The strength of the 8 pass ARB processed material lies between that of the two starting alloys while the ductility decreases after ARB than that of the two constituent starting alloys. These differences in mechanical behavior have been attributed to the microstructural aspects of the individual layer and the fragmentation process. (C) 2011 Elsevier Ltd. All rights reserved.

Homo- or Heterosynthon? A Crystallographic Study on a Series of New Cocrystals Derived from Pyrazinecarboxamide and Various Carboxylic Acids Equipped with Additional Hydrogen Bonding Sites

Four new cocrystals of a well studied active pharmaceutical ingredient (API), namely, pyrazinecarboxamide (PZA), with various monocarboxylic acids equipped with additional hydrogen bonding sites such as vanillic acid (VA), gallic acid (GA), 1-hydroxy-2-naphthoic acid (1HNA), and indole-2-carboxylic acid (I2CA) have been successfully prepared and characterized by FTIR, H-1 NMR, differential scanning calorimetry (DSC), and single crystal and powder X-ray diffraction (SXRD and PXRD, respectively) techniques. In the majority of the cases, preferential occurrence amide amide and acid acid homosynthons has been observed. Since the heterosynthon is energetically preferred to homosynthon, such unusual occurrence of homosynthon in these cocrystals is intriguing.

Probing acid-amide intermolecular hydrogen bonding by NMR spectroscopy and DFT calculations

Benzene carboxylic acids and Benzamide act as their self-complement in molecular recognition to form inter-molecular hydrogen bonded dimers between amide and carboxylic acid groups, which have been investigated by H-1, C-13 and N-15 NMR spectroscopy. Extensive NMR studies using diffusion ordered spectroscopy (DOSY), variable temperature 1D, 2D NMR, established the formation of heterodimers of benzamide with benzoic acid, salicylic acid and phenyl acetic acid in deuterated chloroform solution. Association constants for the complex formation in the solution state have been determined. The results are ascertained by X-ray diffraction in the solid state. Intermolecular interactions in solution and in solid state were found to be similar. The structural parameters obtained by X-ray diffraction studies are compared with those obtained by DFT calculations. (C) 2012 Elsevier B.V. All rights reserved.

Microstructure and texture evolution during accumulative roll bonding of aluminium alloys AA2219/AA5086 composite laminates

Accumulative roll bonding of two aluminium alloys, AA2219 and AA5086 was carried out up to 8 passes. During the course of ARB, the deformation inhomogeneity between the two alloy layers results in interfacial instability after the 4th pass, necking of the AA5086 layers after the 6th pass and fracture along the necked regions after the 7th and 8th pass. The EBSD analysis shows deformation bands along the interfaces after 8 passes of ARB. The ARB-processed materials predominantly show characteristic deformation texture components. The weak texture after the 2nd pass results from the combination of a weakly-textured starting AA2219 layer and a strongly-textured starting AA5086 layer. A strong deformation texture forms due to the high imposed strain after a higher number of ARB passes. Subgrain formation and related shear banding induces copper/S components in the case of the small elongated grains, while planar slip leads to the formation of brass component in the large elongated grains.