The active site behaviour of electrochemically synthesised gold nanomaterials

Even though gold is the noblest of metals, a weak chemisorber and is regarded as being quite inert, it demonstrates significant electrocatalytic activity in its nanostructured form. It is demonstrated here that nanostructured and even evaporated thin films of gold are covered with active sites which are responsible for such activity. The identification of these sites is demonstrated with conventional electrochemical techniques such as cyclic voltammetry as well as a large amplitude Fourier transformed alternating current (FT-ac) method under acidic and alkaline conditions. The latter technique is beneficial in determining if an electrode process is either Faradaic or capacitive in nature. The observed behaviour is analogous to that observed for activated gold electrodes whose surfaces have been severely disrupted by cathodic polarisation in the hydrogen evolution region. It is shown that significant electrochemical oxidation responses occur at discrete potential values well below that for the formation of the compact monolayer oxide of bulk gold and are attributed to the facile oxidation of surface active sites. Several electrocatalytic reactions are explored in which the onset potential is determined by the presence of such sites on the surface. Significantly, the facile oxidation of active sites is used to drive the electroless deposition of metals such as platinum, palladium and silver from their aqueous salts on the surface of gold nanostructures. The resultant surface decoration of gold with secondary metal nanoparticles not only indicates regions on the surface which are rich in active sites but also provides a method to form interesting bimetallic surfaces.

Large amplitude Fourier transformed AC voltammetric investigation of the active state electrochemistry of a copper/aqueous base interface and implications for electrocatalysis

The higher harmonic components available from large-amplitude Fourier-transformed alternating current (FT-ac) voltammetry enable the surface active state of a copper electrode in basic media to be probed in much more detail than possible with previously used dc methods. In particular, the absence of capacitance background current allows low-level Faradaic current contributions of fast electron-transfer processes to be detected; these are usually completely undetectable under conditions of dc cyclic voltammetry. Under high harmonic FT-ac voltammetric conditions, copper electrodes exhibit well-defined and reversible premonolayer oxidation responses at potentials within the double layer region in basic 1.0 M NaOH media. This process is attributed to oxidation of copper adatoms (Cu*) of low bulk metal lattice coordination numbers to surface-bonded, reactive hydrated oxide species. Of further interest is the observation that cathodic polarization in 1.0 M NaOH significantly enhances the current detected in each of the fundamental to sixth FT-ac harmonic components in the Cu*/Cu hydrous oxide electron-transfer process which enables the underlying electron transfer processes in the higher harmonics to be studied under conditions where the dc capacitance response is suppressed; the results support the incipient hydrous oxide adatom mediator (IHOAM) model of electrocatalysis. The underlying quasi-reversible interfacial Cu*/Cu hydrous oxide process present under these conditions is shown to mediate the reduction of nitrate at a copper electrode, while the mediator for the hydrazine oxidation reaction appears to involve a different mediator or active state redox couple. Use of FT-ac voltammetry offers prospects for new insights into the nature of active sites and electrocatalysis at the electrode/solution interface of Group 11 metals in aqueous media.

Decoration of active sites to create bimetallic surfaces and its implication for electrochemical processes

The creation of electrocatalysts based on noble metals has received a significant amount of research interest due to their extensive use as fuel cell catalysts and electrochemical sensors. There have been many attempts to improve the activity of these metals through creating nanostructures, as well as post-synthesis treatments based on chemical, electrochemical, sonochemical and thermal approaches. In many instances these methods result in a material with active surface states, which can be considered to be adatoms or clusters of atoms on the surface that have a low lattice co-ordination number making them more prone to electrochemical oxidation at a wide range of potentials that are significantly less positive than those of their bulk metal counterparts. This phenomenon has been termed pre-monolayer oxidation and has been reported to occur on a range of metallic surfaces. In this work we present findings on the presence of active sites on Pd that has been: evaporated as a thin film; electrodeposited as nanostructures; as well as commercially available Pd nanoparticles supported on carbon. Significantly, advantage is taken of the low oxidation potential of these active sites whereby bimetallic surfaces are created by the spontaneous deposition of Ag from AgNO3 to generate Pd/Ag surfaces. Interestingly this approach does not increase the surface area of the original metal but has significant implications for its further use as an electrode material. It results in the inhibition or promotion of electrocatalytic activity which is highly dependent on the reaction of interest. As a general approach the decoration of active catalytic materials with less active metals for a particular reaction also opens up the possibility of investigating the role of the initially present active sites on the surface and identifying the degree to which they are responsible for electrocatalytic activity.

Improved adhesion of active electrode materials to metal electrode substrates

A battery electrode for a lithium ion battery comprising an elec. conductive substrate having an electrode layer applied thereto, characterized in that the electrode layer includes an org. material having high alky., or an org. material which can be dissolved in org. solvents, or an org. material having an imide group(s) and aminoacetal group(s), or an org. material that chelates with or bonds with a metal substrate or that chelates with or bonds with an active material in the electrode layer. The org. material may be guanidine carbonate. [on SciFinder(R)]

Restorative justice and “Empowerment” : producing and governing active subjects through “Empowering” practices

During the last quarter-century, restorative justice has emerged as a widely utilised response to crime in Western nations. This article, which stems from a Foucauldian genealogy of restorative justice, argues that its embeddedness within the discourse of ‘‘empowerment’’ renders restorative justice a politically acceptable response to crime. ‘‘Empowerment’’, it is argued, is one of many conditions of emergence of restorative justice. The discourse of ‘‘empowerment’’ underpins restorative justice in tangible ways, and has informed legislation and policy in Western jurisdictions. This article seeks to problematise the taken-for-granted nature of this discourse. It argues that the discourse of ‘‘empowerment’’ produces restorative justice subjects who are increasingly governed and governable. As ‘‘empowering’’ restorative practices are targeted towards ‘‘disempowered’’ individuals and communities, concerns are raised about the potential of restorative justice to disproportionately impact upon socially marginalised populations and to increase social exclusion.

Enabling aircraft emergency landings using active visual site detection

The ability to automate forced landings in an emergency such as engine failure is an essential ability to improve the safety of Unmanned Aerial Vehicles operating in General Aviation airspace. By using active vision to detect safe landing zones below the aircraft, the reliability and safety of such systems is vastly improved by gathering up-to-the-minute information about the ground environment. This paper presents the Site Detection System, a methodology utilising a downward facing camera to analyse the ground environment in both 2D and 3D, detect safe landing sites and characterise them according to size, shape, slope and nearby obstacles. A methodology is presented showing the fusion of landing site detection from 2D imagery with a coarse Digital Elevation Map and dense 3D reconstructions using INS-aided Structure-from-Motion to improve accuracy. Results are presented from an experimental flight showing the precision/recall of landing sites in comparison to a hand-classified ground truth, and improved performance with the integration of 3D analysis from visual Structure-from-Motion.

Predictors of initiating and maintaining active commuting to work using transport and public health perspectives in Australia

Objective To identify predictors for initiating and maintaining active commuting (AC) to work following the 2003 Australia's Walk to Work Day (WTWD) campaign. Methods Pre- and post-campaign telephone surveys of a cohort of working age (18–65years) adults (n = 1100, 55% response rate). Two dependent campaign outcomes were assessed: initiating or maintaining AC (i.e., walk/cycle and public transport) on a single day (WTWD), and increasing or maintaining health-enhancing active commuting (HEAC) level (≥ 30min/day) in a usual week following WTWD campaign. Results A significant population-level increase in HEAC (3.9%) was observed (McNemar's χ2 = 6.53, p = 0.01) with 136 (19.0%) achieving HEAC at post campaign. High confidence in incorporating walking into commute, being active pre-campaign and younger age (< 46years) were positively associated with both outcomes. The utility of AC for avoiding parking hassles (AOR = 2.1, 95% CI: 1.2–3.6), for less expense (AOR = 1.8, 95% CI: 1.1–3.1), for increasing one's health (AOR = 2.5, 95% CI: 1.1–5.6) and for clean air (AOR = 2.2, 95% CI: 1.0–4.4) predicted HEAC outcome whereas avoiding the stress of driving (AOR = 2.6, 95% CI: 1.4–5.0) and the hassle of parking predicted the single-day AC. Conclusions Transportation interventions targeting parking and costs could be further enhanced by emphasizing health benefits of AC. AC was less likely to occur among inactive employees.

A high performance feedback active noise control system

In many active noise control (ANC) applications, an online secondary path modelling method that uses a white noise as a training signal is required. This paper proposes a new feedback ANC system. Here we modified both the FxLMS and the VSS-LMS algorithms to raised noise attenuation and modelling accuracy for the overall system. The proposed algorithm stops injection of the white noise at the optimum point and reactivate the injection during the operation, if needed, to maintain performance of the system. Preventing continuous injection of the white noise increases the performance of the proposed method significantly and makes it more desirable for practical ANC systems. Computer simulation results shown in this paper indicate effectiveness of the proposed method.

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.

Environmental factors associated with active living in retirement village residents : findings from an exploratory qualitative enquiry

This exploratory enquiry employs qualitative methods to advance knowledge and understanding of physical environmental attributes related to active living among residents of Australian retirement villages. Six focus groups (n = 51 residents) were held and participants described how their current, and subsequently ideal, retirement village and neighborhood supported active lifestyles. Thematic analysis revealed three key environmental factors associated with active living: a positive social environment within the village; services and facilities provided in the village and wider neighborhood; and the presence of suitable pedestrian infrastructure. The unique discovery that environmental factors of both the retirement village and the surrounding neighborhood were associated with residents’ active living raises many questions for study. Findings informed the development of a survey instrument, and further understanding in this area has the potential to contribute to the design and siting practices of senior housing complexes within neighborhoods.

Exploring socioecological correlates of active living in retirement village residents

This study explored individual, social, and built environmental attributes in and outside of the retirement village setting and associations with various active living outcomes including objectively measured physical activity, specific walking behaviors, and social participation. Residents in Perth, Australia (N = 323), were surveyed on environmental perceptions of the village and surrounding neighborhood, self-reported physical activity, and demographic characteristics and wore accelerometers. Managers (N = 32) were surveyed on village characteristics, and objective neighborhood measures were generated in a Geographic Information System (GIS). Results indicated that built- and social-environmental attributes within and outside of retirement villages were associated with active living among residents; however, salient attributes varied depending on the specific outcome considered. Findings suggest that locating villages close to destinations is important for walking and that locating them close to previous and familiar neighborhoods is important for social participation. Further understanding and consideration into retirement village designs that promote both walking and social participation are needed.

Abstraction : on ambiguity and semiosis in abstract painting

Drawing on the fields of philosophy, phenomenology, art history and theory as well as the candidate's own painting practice, this PhD explores the nature of ambiguity and semiosis in contemporary abstract painting. The thesis demonstrates how the aesthetic qualities of pause and rupture, transition and slippage work emergently to break established clichés, habits and intentions in the experiencing of abstract painting and artistic practice.

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.

Consultant engagement for computer system selection: a pro-active client role in small enterprises

Because of their limited number of senior positions and fewer alternative career paths, small businesses have a more difficult time attracting and retaining skilled information systems (IS) staff and are thus dependent upon external expertise. Small businesses are particularly dependent on outside expertise when first computerizing. Because small businesses suffer from severe financial constraints. it is often difficult to justify the cost of custom software. Hence. for many small businesses, engaging a consultant to help with identifying suitable packaged software and related hardware, is their first critical step toward computerization. This study explores the importance of proactive client involvement when engaging a consultant to assist with computer system selection in small businesses. Client involvement throughout consultant engagement is found to be integral to project success and frequently lacking due to misconceptions of small businesses regarding their role. Small businesses often overestimate the impact of consultant and vendor support in achieving successful computer system selection and implementation. For consultant engagement to be successful, the process must be viewed as being directed toward the achievement of specific organizational results where the client accepts responsibility for direction of the process.