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.

Autonomous forced landing system for light general aviation aircraft in unknown environments

This paper presents a system which enhances the capabilities of a light general aviation aircraft to land autonomously in case of an unscheduled event such as engine failure. The proposed system will not only increase the level of autonomy for the general aviation aircraft industry but also increase the level of dependability. Safe autonomous landing in case of an engine failure with a certain level of reliability is the primary focus of our work as both safety and reliability are attributes of dependability. The system is designed for a light general aviation aircraft but can be extended for dependable unmanned aircraft systems. The underlying system components are computationally efficient and provides continuous situation assessment in case of an emergency landing. The proposed system is undergoing an evaluation phase using an experimental platform (Cessna 172R) in real world scenarios.

Spin-coated carbon

We describe a novel and facile approach to covalently graft molecules containing stable free radicals onto carbon surfaces including graphene, carbon nanotubes, glassy carbon and carbon fibres. The new technique employs a stable aryl nitroxide radical diazonium tetrafluoroborate salt. The salt may be isolated and added to carbon surfaces in solution, suspension or electrochemically and represents a convenient, versatile and highly efficient means to adorn graphitic materials with large numbers of free radical spin systems

A novel protecting group methodology for syntheses using nitroxides

The methoxyamine group represents an ideal protecting group for the nitroxide moiety. It can be easily and selectively introduced in high yield (typically >90%) to a range of functionalised nitroxides using FeSO4.7H2O and H2O2 in DMSO. Its removal is readily achieved under mild conditions in high yield (70-90%) using mCPBA in a Cope-type elimination process.

Traffic state estimation from partial Bluetooth and volume observations : case study in the Brisbane metropolitan area

The application of the Bluetooth (BT) technology to transportation has been enabling researchers to make accurate travel time observations, in freeway and arterial roads. The Bluetooth traffic data are generally incomplete, for they only relate to those vehicles that are equipped with Bluetooth devices, and that are detected by the Bluetooth sensors of the road network. The fraction of detected vehicles versus the total number of transiting vehicles is often referred to as Bluetooth Penetration Rate (BTPR). The aim of this study is to precisely define the spatio-temporal relationship between the quantities that become available through the partial, noisy BT observations; and the hidden variables that describe the actual dynamics of vehicular traffic. To do so, we propose to incorporate a multi- class traffic model into a Sequential Montecarlo Estimation algorithm. Our framework has been applied for the empirical travel time investigations into the Brisbane Metropolitan region.

Perceptions of climate change and trust in information providers in rural Australia

Disagreement within the global science community about the certainty and causes of climate change has led the general public to question what to believe and who to trust on matters related to this issue. This paper reports on qualitative research undertaken with Australian residents from two rural areas to explore their perceptions of climate change and trust in information providers. While overall, residents tended to agree that climate change is a reality, perceptions varied in terms of its causes and how best to address it. Politicians, government, and the media were described as untrustworthy sources of information about climate change, with independent scientists being the most trusted. The vested interests of information providers appeared to be a key reason for their distrust. The findings highlight the importance of improved transparency and consultation with the public when communicating information about climate change and related policies.

Mesoporous titania microspheres composed of exposed active faceted nanosheets and their catalytic activities for solvent-free synthesis of azoxybenzenes

Mesoporous titania microspheres composed of nanosheets with exposed active facets were prepared by hydrothermal synthesis in the presence of hexafluorosilicic acid. They exhibited superior catalytic activity in the solvent-free synthesis of azoxybenzene by oxidation of aniline and could be used for 7 cycles with slight loss of activity.

An international survey of daily disposable contact lens prescribing

Purpose The aim was to determine the extent of daily disposable contact lens prescribing worldwide and to characterise the associated demographics and fitting patterns. Methods Up to 1,000 survey forms were sent to contact lens fitters in up to 40 countries between January and March every year for five consecutive years (2007 to 2011). Practitioners were asked to record data relating to the first 10 contact lens fits or refits performed after receiving the survey form. Survey data collected since 1996 were also analysed for seven nations to assess daily disposable lens fitting trends since that time. Results Data were collected in relation to 97,289 soft lens fits, of which 23,445 (24.1 per cent) were with daily disposable lenses and 73,170 (75.9 per cent) were with reusable lenses. Daily disposable lens prescribing ranged from 0.6 per cent of all soft lenses in Nepal to 66.2 per cent in Qatar. Compared with reusable lens fittings, daily disposable lens fittings can be characterised as follows: older age (30.0 ± 12.5 versus 29.3 ± 12.3 years for reusable lenses); males are over-represented; a greater proportion of new fits versus refits; 85.9 per cent hydrogel; lower proportion of toric and presbyopia designs and a higher proportion of part-time wear. There has been a continuous increase in daily disposable lens prescribing between 1996 and 2011. The proportion of daily disposable lens fits (as a function of all soft lens fits) is positively related to the gross domestic product at purchasing power parity per capita (r2 = 0.55, F = 46.8, p < 0.0001). Conclusions The greater convenience and other benefits of daily disposable lenses have resulted in this modality capturing significant market share. The contact lens field appears to be heading toward a true single-use-only, disposable lens market.

Sustainable creative career development pathways for young people in Tanzania : a case study

Tanzania has a rich and diverse cultural history based in community cultural life. However, at present, young people have limited opportunity to exploit this richness of traditional knowledge and engage in creative jobs as their means of future sustainable employment. Hence, the significant challenge remains: how to integrate and enhance the traditional knowledge in a learning strategy, while there is no “inter-ministerial action and institutional mechanisms” (United Nations 2008, 33-35) to promote creative employment for young people. This article reports on a case study that examined how the two Ministries of Culture and Education might work together to support Tanzania’s young people to secure, and engage successfully in creative jobs. The case study employed mixed methods, incorporating questionnaires, interviews and focus groups. The study was undertaken in Dar-Es-Salaam, Mwanza, Bagamoyo, Dodoma, Lindi and Morogoro from July to October, 2012. This paper discusses some of the issues and argues that there is no practical utilization of traditional knowledge and skills in “putting education to work” (UNESCO 2012, 170) for the better prospects of young people and to reveal the story of their lives. Although this study is specific to Tanzania, the case may also apply to other developing countries.

Photocatalysis on supported gold and silver nanoparticles under ultraviolet and visible light irradiation

Studies of the optical properties and catalytic capabilities of noble metal nanoparticles (NPs), such as gold (Au) and silver (Ag), have formed the basis for the very recent fast expansion of the field of green photocatalysis: photocatalysis utilizing visible and ultraviolet light, a major part of the solar spectrum. The reason for this growth is the recognition that the localised surface plasmon resonance (LSPR) effect of Au NPs and Ag NPs can couple the light flux to the conduction electrons of metal NPs, and the excited electrons and enhanced electric fields in close proximity to the NPs can contribute to converting the solar energy to chemical energy by photon-driven photocatalytic reactions. Previously the LSPR effect of noble metal NPs was utilized almost exclusively to improve the performance of semiconductor photocatalysts (for example, TiO2 and Ag halides), but recently, a conceptual breakthrough was made: studies on light driven reactions catalysed by NPs of Au or Ag on photocatalytically inactive supports (insulating solids with a very wide band gap) have demonstrated that these materials are a class of efficient photocatalysts working by mechanisms distinct from those of semiconducting photocatalysts. There are several reasons for the significant photocatalytic activity of Au and Ag NPs. (1) The conduction electrons of the particles gain the irradiation energy, resulting in high energy electrons at the NP surface which is desirable for activating molecules on the particles for chemical reactions. (2) In such a photocatalysis system, both light harvesting and the catalysing reaction take place on the nanoparticle, and so charge transfer between the NPs and support is not a prerequisite. (3) The density of the conduction electrons at the NP surface is much higher than that at the surface of any semiconductor, and these electrons can drive the reactions on the catalysts. (4) The metal NPs have much better affinity than semiconductors to many reactants, especially organic molecules. Recent progress in photocatalysis using Au and Ag NPs on insulator supports is reviewed. We focus on the mechanism differences between insulator and semiconductor-supported Au and Ag NPs when applied in photocatalytic processes, and the influence of important factors, light intensity and wavelength, in particular estimations of light irradiation contribution, by calculating the apparent activation energies of photo reactions and thermal reactions.

Controlling whole blood activation and resultant clot properties by carboxyl and alkyl functional groups on material surfaces : a possible therapeutic approach for enhancing bone healing

Most research virtually ignores the important role of a blood clot in supporting bone healing. In this study, we investigated the effects of surface functional groups carboxyl and alkyl on whole blood coagulation, complement activation and blood clot formation. We synthesised and tested a series of materials with different ratios of carboxyl (–COOH) and alkyl (–CH3, –CH2CH3 and –(CH2)3CH3) groups. We found that surfaces with –COOH/–(CH2)3CH3 induced a faster coagulation activation than those with –COOH/– CH3 and –CH2CH3, regardless of the –COOH ratios. An increase in –COOH ratios on –COOH/–CH3 and –CH2CH3 surfaces decreased the rate of coagulation activation. The pattern of complement activation was entirely similar to that of surface-induced coagulation. All material coated surfaces resulted in clots with thicker fibrin in a denser network at the clot/material interface and a significantly slower initial fibrinolysis when compared to uncoated glass surfaces. The amounts of platelet-derived growth factor-AB (PDGF-AB) and transforming growth factor-b (TGF-b1) released from an intact clot were higher than a lysed clot. The release of PDGF-AB was found to be correlated with the fibrin density. This study demonstrated that surface chemistry can significantly influence the activation of blood coagulation and complement system, resultant clot structure, susceptibility to fibrinolysis as well as release of growth factors, which are important factors determining the bone healing process.

From single crystal surfaces to single atoms : investigating active sites in electrocatalysis

Electrocatalytic processes will undoubtedly be at the heart of energising future transportation and technology with the added importance of being able to create the necessary fuels required to do so in an environmentally friendly and cost effective manner. For this to be successful two almost mutually exclusive surface properties need to be reconciled, namely producing highly active/reactive surface sites that exhibit long term stability. This article reviews the various approaches which have been undertaken to study the elusive nature of these active sites on metal surfaces which are considered as adatoms or clusters of adatoms with low coordination number. This includes the pioneering studies at extended well defined stepped single crystal surfaces using cyclic voltammetry up to the highly sophisticated in situ electrochemical imaging techniques used to study chemically synthesised nanomaterials. By combining the information attained from single crystal surfaces, individual nanoparticles of defined size and shape, density functional theory calculations and new concepts such as mesoporous multimetallic thin films and single atom electrocatalysts new insights into the design and fabrication of materials with highly active but stable active sites can be achieved. The area of electrocatalysis is therefore not only a fascinating and exciting field in terms of realistic technological and economical benefits but also from the fundamental understanding that can be acquired by studying such an array of interesting materials.

A computational study of carbon dioxide adsorption on solid boron

Capturing and sequestering carbon dioxide (CO2) can provide a route to partial mitigation of climate change associated with anthropogenic CO2 emissions. Here we report a comprehensive theoretical study of CO2 adsorption on two phases of boron, α-B12 and γ-B28. The theoretical results demonstrate that the electron deficient boron materials, such as α-B12 and γ-B28, can bond strongly with CO2 due to Lewis acid-base interactions because the electron density is higher on their surfaces. In order to evaluate the capacity of these boron materials for CO2 capture, we also performed calculations with various degrees of CO2 coverage. The computational results indicate CO2 capture on the boron phases is a kinetically and thermodynamically feasible process, and therefore from this perspective these boron materials are predicted to be good candidates for CO2 capture.

Strain engineering of selective chemical adsorption on monolayer MoS2

Nanomaterials are prone to influence by chemical adsorption because of their large surface to volume ratios. This enables sensitive detection of adsorbed chemical species which, in turn, can tune the property of the host material. Recent studies discovered that single and multi-layer molybdenum disulfide (MoS2) films are ultra-sensitive to several important environmental molecules. Here we report new findings from ab inito calculations that reveal substantially enhanced adsorption of NO and NH3 on strained monolayer MoS2 with significant impact on the properties of the adsorbates and the MoS2 layer. The magnetic moment of adsorbed NO can be tuned between 0 and 1 μB; strain also induces an electronic phase transition between half-metal and metal. Adsorption of NH3 weakens the MoS2 layer considerably, which explains the large discrepancy between the experimentally measured strength and breaking strain of MoS2 films and previous theoretical predictions. On the other hand, adsorption of NO2, CO, and CO2 is insensitive to the strain condition in the MoS2 layer. This contrasting behavior allows sensitive strain engineering of selective chemical adsorption on MoS2 with effective tuning of mechanical, electronic, and magnetic properties. These results suggest new design strategies for constructing MoS2-based ultrahigh-sensitivity nanoscale sensors and electromechanical devices.

Numerical modelling of load bearing light gauge steel frame wall systems exposed to realistic design fires

Fire safety has become an important part in structural design due to the ever increasing loss of properties and lives during fires. Conventionally the fire rating of load bearing wall systems made of Light gauge Steel Frames (LSF) is determined using fire tests based on the standard time-temperature curve in ISO834 [1]. However, modern commercial and residential buildings make use of thermoplastic materials, which mean considerably high fuel loads. Hence a detailed fire research study into the fire performance of LSF walls was undertaken using realistic design fire curves developed based on Eurocode parametric [2] and Barnett’s BFD [3] curves using both full scale fire tests and numerical studies. It included LSF walls without cavity insulation, and the recently developed externally insulated composite panel system. This paper presents the details of finite element models developed to simulate the full scale fire tests of LSF wall panels under realistic design fires. Finite element models of LSF walls exposed to realistic design fires were developed, and analysed under both transient and steady state fire conditions using the measured stud time-temperature curves. Transient state analyses were performed to simulate fire test conditions while steady state analyses were performed to obtain the load ratio versus time and failure temperature curves of LSF walls. Details of the developed finite element models and the results including the axial deformation and lateral deflection versus time curves, and the stud failure modes and times are presented in this paper. Comparison with fire test results demonstrate the ability of developed finite element models to predict the performance and fire resistance ratings of LSF walls under realistic design fires.