Process and catalysts for the methanation of oxides of carbon

The present invention is directed to catalysts for the conversion of oxides of carbon to methane and/or other hydrocarbons and to precursors of such catalysts. The catalyst precursors include one or more refractory oxides selected from the group consisting of rare earth oxides and rare earth contg. perovskites, the precursor including nickel or nickel cations sufficient for a catalyst obtainable by reducing the precursor to be capable of at least partially reducing an oxide of carbon to a hydrocarbon product. Processes for the prepn. of such catalysts and catalyst precursors are also disclosed, as are processes for the conversion of oxides of carbon to methane and/or other hydrocarbons. [on SciFinder(R)]

Reusable surface confined semi-conducting metal-TCNQ and metal-TCNQF4 catalysts for electron transfer reactions

The synthesis of organic semiconducting materials based on silver and copper-TCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) and their fluorinated analogues has received a significant amount of attention due to their potential use in organic electronic applications. However, there is a scarcity in the identification of different applications for which these interesting materials may be suitable candidates. In this work, we address this by investigating the catalytic properties of such materials for the electron transfer reaction between ferricyanide and thiosulphate ions in aqueous solution, which to date has been almost solely limited to metallic nanomaterials. Significantly it was found that all the materials investigated, namely CuTCNQ, AgTCNQ, CuTCNQF4 and AgTCNQF4, were catalytically active and, interestingly, the fluorinated analogues were superior. AgTCNQF4 demonstrated the highest activity and was tested for its stability and re-usability for up to 50 cycles without degradation in performance. The catalytic reaction was monitored via UV-vis spectroscopy and open circuit potential versus time measurements, as well as an investigation of the transport properties of the films via electrochemical impedance spectroscopy. It is suggested that morphology and bulk conductivity are not the limiting factors, but rather the balance between the accumulated surface charge from electron injection via thiosulphate ions on the catalyst surface and transfer to the ferricyanide ions which controls the reaction rate. The facile fabrication of re-usable surface confined organic materials that are catalytically active may have important uses for many more electron transfer reactions.

Perdido ties together Shell digital oilfield technologies

Located in the Gulf of Mexico in nearly 8,000 ft of water, the Perdido project is the deepest spar application to date in the world and Shell’s first fully integrated application of its inhouse digital oilfield technology— called “Smart Field”—in the Western hemisphere. Developed by Shell on behalf of partners BP and Chevron, the spar and the subsea equipment connected to it will eventually capture about an order of magnitude more data than is collected from any other Shelldesigned and -managed development operating in the Gulf of Mexico. This article describes Shell’s digital oilfield design philosophy, briefly explains the five design elements that underpin “smartness” in Shell’s North and South American operations and sheds light on the process by which a highly customized digital oilfield development and management plan was put together for Perdido. Although Perdido is the first instance in North and South America in which these design elements and processes were applied in an integrated way, all of Shell’s future new developments in the Western hemisphere are expected to follow the same overarching design principles. Accordingly, this article uses Perdido as a real-world example to outline the high-level details of Shell’s digital oilfield design philosophy and processes.

Electrochemical formation of Cu/Ag surfaces and their applicability as heterogeneous catalysts

In this work the electrochemical formation of porous Cu/Ag materials is reported via the simple and quick method of hydrogen bubble templating. The bulk and surface composition ratio between Ag and Cu was varied in a systematic manner and was readily controlled by the concentration of precursor metal salts in the electrolyte. The incorporation of Ag within the Cu scaffold only affected the formation of well-defined pores at high Ag loading whereas the internal pore wall structure gradually transformed from dendritic to cube like and finally needle like structures, which was due to the concomitant formation of Cu2O within the structure. The materials were characterised by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Their surface properties were further investigated by surface enhanced Raman spectroscopy (SERS) and electrochemically probed by recording the hydrogen evolution reaction (HER) which is highly sensitive to the nature of the surface. The effect of surface composition was then investigated for its influence on two catalytic reactions namely the reduction of ferricyanide ions with thiosulphate ions and the reduction of 4-nitrophenol with NaBH4 in aqueous solution where it was found that the presence of Ag had a beneficial effect in both cases but more so in the case of nitrophenol reduction. It is believed that this material may have many more potential applications in the area of catalysis, electrocatalysis and photocatalysis.

Effects of joint thickness, adhesion and web shells to the face shell bedded concrete masonry loaded in compression

The Australian masonry standard allows either prism tests or correction factors based on the block height and mortar thickness to evaluate masonry compressive strength. The correction factor helps the taller units with conventional 10 mm mortar being not disadvantaged due to size effect. In recent times, 2-4 mm thick, high-adhesive mortars and H blocks with only the mid-web shell are used in masonry construction. H blocks and thinner and higher adhesive mortars have renewed interest of the compression behaviour of hollow concrete masonry and hence is revisited in this paper. This paper presents an experimental study carried out to examine the effects of the thickness of mortar joints, the type of mortar adhesives and the presence of web shells in the hollow concrete masonry prisms under axial compression. A non-contact digital image correlation technique was used to measure the deformation of the prisms and was found adequate for the determination of strain fi eld of the loaded face shells subjected to axial compression. It is found that the absence of end web shells lowers the compressive strength and stiffness of the prisms and the thinner and higher adhesive mortars increase the compressive strength and stiffness, while lowering the Poisson's ratio. © Institution of Engineers Australia, 2013.

Nb2O5 Schottky based ethanol vapour sensors : effect of metallic catalysts

The aim of this paper is to compare the performances of the highly porous Nb2O5 Schottky based sensors formed using different catalytic metals for ethanol vapour sensing. The fabricated sensors consist of a fairly ordered nano-vein like porous Nb2O5 prepared via an elevated temperature anodization method. Subsequently, Pt, Pd and Au were sputtered as both Schottky contacts and catalysts for the comparative studies. These metals are chosen as they have large work functions in comparison to the electron affinity of the anodized Nb2O5. It is demonstrated that the device based on Pd/Nb2O5 Schottky contact has the highest sensitivity amongst the developed sensors. The sensing behaviors were studied in terms of the Schottky barrier height variations and properties of the metal catalysts.

Numerical investigation into the buckling behavior of advanced grid stiffened composite cylindrical shell

Advanced grid stiffened composite cylindrical shell is widely adopted in advanced structures due to its exceptional mechanical properties. Buckling is a main failure mode of advanced grid stiffened structures in engineering, which calls for increasing attention. In this paper, the buckling response of advanced grid stiffened structure is investigated by three different means including equivalent stiffness model, finite element model and a hybrid model (H-model) that combines equivalent stiffness model with finite element model. Buckling experiment is carried out on an advanced grid stiffened structure to validate the efficiency of different modeling methods. Based on the comparison, the characteristics of different methods are independently evaluated. It is arguable that, by considering the defects of material, finite element model is a suitable numerical tool for the buckling analysis of advanced grid stiffened structures.

Physisorption-induced electron scattering on the surface of carbon-metal core-shell nanowire arrays for hydrogen sensing

Palladium is sputtered on multi-walled carbon nanotube forests to form carbon-metal core-shell nanowire arrays. These hybrid nanostructures exhibited resistive responses when exposed to hydrogen with an excellent baseline recovery at room temperature. The magnitude of the response is shown to be tuneable by an applied voltage. Unlike the charge-transfer mechanism commonly attributed to Pd nanoparticle-decorated carbon nanotubes, this demonstrates that the hydrogen response mechanism of the multi-walled carbon nanotube-Pd core-shell nanostructure is due to the increase in electron scattering induced by physisorption of hydrogen. These hybrid core-shell nanostructures are promising for gas detection in hydrogen storage applications.

Control of core-shell structure and elemental composition of binary quantum dots

The possibility of initial stage control of the elemental composition and core/shell structure of binary SiC quantum dots by optimizing temporal variation of Si and C incoming fluxes and surface temperatures is shown via hybrid numerical simulations. Higher temperatures and influxes encourage the formation of a stoichiometric outer shell over a small carbon-enriched core, whereas lower temperatures result in a larger carbon-enriched core, Si-enriched undershell, and then a stoichiometric SiC outer shell. This approach is generic and is applicable to a broad range of semiconductor materials and nanofabrication techniques. © 2007 American Institute of Physics.

Catalytic role of pre-adsorbed CO in platinum-based catalysts : the reduction of SO 2 by CO on Pt l Au m (CO) n

Using density functional theory, we have investigated the catalytic properties of bimetallic complex catalysts PtlAum(CO)n (l + m = 2, n = 1–3) in the reduction of SO2 by CO. Due to the strong coupling between the C-2p and metal 5d orbitals, pre-adsorption of CO molecules on the PtlAum is found to be very effective in not only reducing the activation energy, but also preventing poisoning by sulfur. As result of the coupling, the metal 5d band is broadened and down-shifted, and charge is transferred from the CO molecules to the PtlAum. As SO2 is adsorbed on the catalyst, partial charge moves to the anti-σ bonding orbitals between S and O in SO2, weakening the S–O bond strength. This effect is enhanced by pre-adsorbing up to three CO molecules, therefore the S–O bonds become vulnerable. Our results revealed the mechanism of the excellent catalytic properties of the bimetallic complex catalysts.

Museums as urban catalysts : the role of urban design in flagship cultural development

A long-held urban redevelopment strategy has been the investment in flagship cultural projects—large-scale, iconic museums and arts centres that are intended to enhance the city image while catalyzing private sector investment and attracting tourists to the surrounding area. This paper concentrates on an aspect of the flagship cultural strategy that has received surprisingly little focused attention—the role that urban design and context play in realizing project outcomes. The analysis concentrates on two established flagship museums in Los Angeles and San Jose, California. The research demonstrates that certain urban design characteristics can negatively affect the ability of a project to attract visitors and generate commercial activity. However, at the same time, factors beyond the local context may be an overriding factor in project outcomes thus calling into question the concept of cultural catalyst.

Multi-ciphersuite security of the Secure Shell (SSH) protocol

The Secure Shell (SSH) protocol is widely used to provide secure remote access to servers, making it among the most important security protocols on the Internet. We show that the signed-Diffie--Hellman SSH ciphersuites of the SSH protocol are secure: each is a secure authenticated and confidential channel establishment (ACCE) protocol, the same security definition now used to describe the security of Transport Layer Security (TLS) ciphersuites. While the ACCE definition suffices to describe the security of individual ciphersuites, it does not cover the case where parties use the same long-term key with many different ciphersuites: it is common in practice for the server to use the same signing key with both finite field and elliptic curve Diffie--Hellman, for example. While TLS is vulnerable to attack in this case, we show that SSH is secure even when the same signing key is used across multiple ciphersuites. We introduce a new generic multi-ciphersuite composition framework to achieve this result in a black-box way.

A comparison of lungworm faecal larval counts and trichostrongyloid faecal egg counts between Red Deer (Cervus elaphus) and Red DeerXWapiti F1 hybrids.

To determine if breed differences in susceptibility to trichostrongyloid and lungworm infection exist, two groups of weaner deer containing seven red deer and red deer X wapiti F1 hybrids were compared using faecal egg counts and faecal larval counts. All animals were run on the same pasture at the same time and treated with the same anthelmintics at the same time. Results indicated that there were significant differences between red deer and red deer X wapiti hybrids, with red deer having higher faecal lungworm counts and red deer X wapiti hybrids having significantly higher faecal egg counts. It is likely that these differences were due to breed. Differences in the efficacy of anthelmintic treatments were also noted between the two groups, with oral oxfendazole being less effective at reducing faecal lungworm counts in red deer X wapiti hybrids than red deer.

Effects of mesostructured silica catalysts on the depolymerization of organosolv lignin fractionated from woody eucalyptus

Isolated and purified organosolv eucalyptus wood lignin was depolymerized at different temperatures with and without mesostructured silica catalysts (i.e., SBA-15, MCM-41, ZrO2-SBA-15 and ZrO2-MCM-41). It was found that at 300 oC for 1 h with a solid/liquid ratio of 0.0175/1 (w/v), the SBA-15 catalyst with high acidity gave the highest syringol yield of 23.0% in a methanol/water mixture (50/50, wt/wt). Doping with ZrO2 over these catalysts did not increase syringol yield, but increased the total amount of solid residue. Gas chromatography-mass spectrometry (GC-MS) also identified other main phenolic compounds such as 1-(4-hydroxy-3,5-dimethoxyphenyl)-ethanone, 1,2-benzenediol, and 4-hydroxy-3,5-dimethoxy-benzaldehyde. Analysis of the lignin residues with Fourier transform-Infrared spectroscopy (FT-IR) indicated decreases in the absorption bands intensities of OH group, C-O stretching of syringyl ring and aromatic C-H deformation of syringol unit, and an increase in band intensities associated with the guaiacyl ring, confirming the type of products formed.

Art and science as creative catalysts

Science, Art and Science Art collaborations are generally presented and understood in terms of their products. We argue that the process of Science art can be a significant, even principal benefit of these collaborations, even though it may be largely invisible to anyone other than the collaborators. Hosting the Centenary of Canberra Science Art Commission at the Commonwealth Scientific and Industrial Research Organisation (CSIRO) has shown us that while Science and Art pursue orthogonal dimensions of creativity and innovation, collaborators can combine these directions to access new areas of imagination and ideas.