Unambiguous atomic structural determination of single-walled carbon nanotubes by electron diffraction

We introduce a novel non-dimensional “intrinsic layer-line spacing” concept for electron diffraction analysis of single-walled carbon nanotubes (SWCNTs). Accordingly, we develop a unique method for direct determination of chiral indices (n, m) of the carbon nanotubes from their electron diffraction patterns (EDPs). The new method is totally calibration-free. Errors due to the nanotube inclination are specified. The tilt angle of the carbon nanotube with respect to the incident electron beam is simultaneously evaluated, thus the effect of the tube tilting is compensated for in the (n, m) determination. Several effective procedures are proposed to cross-check the results by using abundant information contained in the diffraction patterns. The efficiency of the method is demonstrated on both simulated and experimental diffraction patterns from single-walled nanotubes. The technique can be extended to structural analysis of nanotubes of structure similar to carbon nanotubes, such as boron nitride nanotubes.     

The kinetics of the silver (I)/silver (II) couple at a platinum electrode in perchloric and nitric acids

The kinetics of the silver (I)/silver (II) couple have been studied in 3 M nitric acid and 3 M perchloric acid at a platinum electrode. It has been found that silver (II) can be produced in high current yields in a fast electrode reaction although the conversion of silver (I) to silver (II) is limited by the chemical reaction of silver (II) with water. It has also been shown that silver (I) can successfully be used as a catalyst or current carrier in the anodic oxidation of organic and inorganic substrates.     

Variable temperature13C MAS NMR of KFe2Mn(CO)12 in the solid state and as aCatalyst precursor on a carbon support

Variable temperature¹³C MAS NMR spectra are reported for¹³CO-enriched KFe₂Mn(CO)₁₂ as a solid and also as dispersed clusters on a carbon support. The spectrum of KFe₂Mn(CO)₁₂ at 300 K agrees with the proposed structure for this cluster and shows that the cluster is static. Two bridging carbonyl resonances are clearly resolved and, by comparison with¹³C MAS NMR spectra of Mn₂(CO)₁₀ and Fe₂(CO)₉, all terminal resonances for the cluster can be assigned. When the cluster is supported on carbon, two broad resonances are observed at room temperature which are assignable to KFe₂Mn(CO)₁₂ and a decomposition product, Mn₂(CO)₁₀. The carbonyl ligands in both supported clusters are completely averaged, and KFe₂Mn(CO)₁₂ on the carbon surface demonstrates fluxional behavior similar to that observed for the cluster in solution. For this fluxional process, activation energies of 0.6 kcal/mol and 0.5 kcal/mol are estimated for carbon-supported KFe₂Mn(CO)₁₂ and Mn₂(CO)₁₀, respectively.     

Carbon nanotubes and onions from carbon monoxide using Ni(acac)2 and Cu(acac)2 as catalyst precursors

New catalyst precursors (copper and nickel acetylacetonates) have been used successfully for the synthesis of carbon nanotubes and onion particles from carbon monoxide. Catalyst nanoparticles and carbon products were produced by metal-organic precursor vapour decomposition and catalytic disproportionation of carbon monoxide in a laminar flow reactor at temperatures between 705 and 1216 °C. Carbon nanotubes (CNTs) were formed in the presence of nickel particles at 923-1216 °C. The CNTs were single-walled, 1-3 nm in diameter and up to 90 nm long. Hollow carbon onion particles (COPs) were produced in the presence of copper particles at 1216 °C. The COPs were from 5 to 30 nm in diameter and consisted of several concentric carbon layers surrounding a hollow core. The results of computational fluid dynamics calculations to determine the temperature and velocity profiles and mixing conditions of the species in the reactor are presented. The mechanisms for the formation of both CNTs and COPs are discussed on the basis of the experimental and computational results.     

Dense subgraph maintenance under streaming edge weight updates for real-time story identification

Recent years have witnessed an unprecedented proliferation of social media. People around the globe author, everyday, millions of blog posts, social network status updates, etc. This rich stream of information can be used to identify, on an ongoing basis, emerging stories, and events that capture popular attention. Stories can be identified via groups of tightly coupled real-world entities, namely the people, locations, products, etc, that are involved in the story. The sheer scale and rapid evolution of the data involved necessitate highly efficient techniques for identifying important stories at every point of time. The main challenge in real-time story identification is the maintenance of dense subgraphs (corresponding to groups of tightly coupled entities) under streaming edge weight updates (resulting from a stream of user-generated content). This is the first work to study the efficient maintenance of dense subgraphs under such streaming edge weight updates. For a wide range of definitions of density, we derive theoretical results regarding the magnitude of change that a single edge weight update can cause. Based on these, we propose a novel algorithm, DynDens, which outperforms adaptations of existing techniques to this setting and yields meaningful, intuitive results. Our approach is validated by a thorough experimental evaluation on large-scale real and synthetic datasets.     

Solvent-free oxidation of benzyl alcohol using titania-supported gold–palladium catalysts: Effect of Au–Pd ratio on catalytic performance

The oxidation of benzyl alcohol with molecular oxygen under solvent-free conditions has been investigated using a range of titania-supported Au–Pd alloy catalysts to examine the effect of the Au–Pd ratio on the conversion and selectivity. The catalysts have been compared at high reaction temperature (160 °C) as well as at 100 °C, to determine the effect on selectivity since at lower reaction temperature the range of by-products that are formed are limited. Under these conditions the 2.5 wt.% Au–2.5 wt.% Pd/TiO₂ was found to be the most active catalyst, whereas the Au/TiO₂ catalyst demonstrated the highest selectivity to benzaldehyde. Toluene, formed via either a hydrogen transfer process or an oxygen transfer process, was observed as a major by-product under these forcing conditions.     

Solvent free liquid phase oxidation of benzyl alcohol using Au supported catalysts prepared using a sol immobilization technique

Solvent free oxidation of benzyl alcohol was investigated in the absence of a base using Au catalysts prepared by sol immobilization on titania and carbon supports. Comparison between the Au supported catalysts revealed that activity and distribution of products was dependent on the nature of support and heat treatment. Specifically, heat pre-treatment of the Au catalysts has a beneficial effect in terms of activity, but is detrimental in terms of selectivity to the benzaldehyde. We conclude that sol immobilization is a suitable technique for preparing gold catalysts with small particle size and narrow particle size distributions and very high activity and selectivity for benzyl alcohol oxidation.     

Modeling nonisothermal impregnation of fibrous media with reactive polymer resin

The manufacture of polymer composites through resin transfer molding (RTM) or structural reaction injection molding (SRIM) involves the impregnation of a fibrous reinforcement in a mold cavity with a reactive polymer resin. The design of RTM and SRIM operations requires an understanding of the various parameters, such as materials properties, mold geometry, and mold filling conditions, that affect the resin impregnation process. Modeling provides a potential tool for analyzing the relationships among the important parameters. The present work provides the physical model and finite element formulations for simulating the mold filling stage. Resin flow through the fibers is modeled using two-dimensional Darcian flow. Simultaneous resin reaction and heat transfer among resin, mold walls, and fibers are considered in the model. The proposed technique emphasizes the use of the least squares finite element method to solve the convection dominated mass and energy equations for the resin. Excellent numerical stability of the proposed technique provides a powerful numerical method for the modeling of polymer processing systems characterized by convection dominated transport equations. Results from example numerical studies for SRIM of polyurethane/glass fiber composites were presented to illustrate the application of the proposed model and numerical scheme.     

Direct synthesis of hydrogen peroxide from H2 and O2 using zeolite-supported Au catalysts

The direct synthesis of hydrogen peroxide from H₂ and O₂ using zeolite-supported Au catalysts is described and their activity is contrasted with silica- and alumina-supported Au catalysts. Two zeolites were investigated, ZSM-5 and zeolite Y. The effect of calcination of these catalysts is studied and it is found that for uncalcined catalysts high rates of hydrogen peroxide formation are observed, but these catalysts are unstable and lose Au during use. Consequently, reuse of these catalysts leads to lower rates of hydrogen peroxide formation. However, catalysts calcined at 400 °C are more stable and can be reused without loss of gold. The use of zeolites as a support for Au gives comparable rates of hydrogen peroxide formation to alumina-supported Au catalysts and higher rates when compared with silica-supported catalysts. prepared using a similar method. Zeolite Y-supported catalysts are more active than ZSM-5-supported catalysts for the stable calcined materials. It is considered that the overall activity of these supported catalysts may be related to the aluminium content as the activity increases with increasing aluminium content.