Generation of active surface states of gold and the role of such states in electrocatalysis

The cyclic voltammetry behaviour of gold in aqueous media is often regarded in very simple terms as a combination of two distinct processes, double layer charging/discharging and monolayer oxide formation/removal. This view is questioned here on the basis of both the present results and earlier independent data by other authors. It was demonstrated in the present case that both severe cathodization or thermal pretreatment of polycrystalline gold in acid solution resulted in the appearance of substantial Faradaic responses in the double layer region. Such anamolous behaviour, as outlined recently also for other metals, is rationalized in terms of the presence of active metal atoms (which undergo premonolayer oxidation) at the electrode surface. Such behaviour, which is also assumed to correspond to that of active sites on conventional gold surfaces, is assumed to be of vital importance in electrocatalysis; in many instances the latter process is also quite marked in the double layer region.

Surface waves in strongly irradiated dusty plasmas

High-frequency surface waves at the interface between two dusty plasmas subject to radiation are considered. Ultraviolet radiation with energy flux larger than the photoelectric work function of the dust surface causes photoemission of electrons. The dust charge and the overall charge balance of the plasma are thus modified. The dispersion properties of the surface waves are investigated for three parameter regimes distinguished by the charging mechanisms in the two plasmas. It is shown that photoemission can significantly affect the plasma and the surface waves.

Surface engineering of reduced graphene oxide for controllable ambipolar flash memories

Tunable charge-trapping behaviors including unipolar charge trapping of one type of charge carrier and ambipolar trapping of both electrons and holes in a complementary manner is highly desirable for low power consumption multibit flash memory design. Here, we adopt a strategy of tuning the Fermi level of reduced graphene oxide (rGO) through self-assembled monolayer (SAM) functionalization and form p-type and n-type doped rGO with a wide range of manipulation on work function. The functionalized rGO can act as charge-trapping layer in ambipolar flash memories, and a dramatic transition of charging behavior from unipolar trapping of electrons to ambipolar trapping and eventually to unipolar trapping of holes was achieved. Adjustable hole/electron injection barriers induce controllable Vth shift in the memory transistor after programming operation. Finally, we transfer the ambipolar memory on flexible substrates and study their charge-trapping properties at various bending cycles. The SAM-functionalized rGO can be a promising candidate for next-generation nonvolatile memories.

Uncoupled surface spin induced exchange bias in α-MnO 2 nanowires

We have studied the microstructure, surface states, valence fluctuations, magnetic properties, and exchange bias effect in MnO2 nanowires. High purity α-MnO 2 rectangular nanowires were synthesized by a facile hydrothermal method with microwave-assisted procedures. The microstructure analysis indicates that the nanowires grow in the [0 0 1] direction with the (2 1 0) plane as the surface. Mn3+ and Mn2+ ions are not found in the system by X-ray photoelectron spectroscopy. The effective magnetic moment of the manganese ions fits in with the theoretical and experimental values of Mn4+ very well. The uncoupled spins in 3d3 orbitals of the Mn 4+ ions in MnO 6 octahedra on the rough surface are responsible for the net magnetic moment. Spin glass behavior is observed through magnetic measurements. Furthermore, the exchange bias effect is observed for the first time in pure α-MnO2 phase due to the coupling of the surface spin glass with the antiferromagnetic α-MnO2 matrix. These α-MnO2 nanowires, with a spin-glass-like behavior and with an exchange bias effect excited by the uncoupled surface spins, should therefore inspire further study concerning the origin, theory, and applicability of surface structure induced magnetism in nanostructures.

Diagnosing dry eye with dynamic-area high-speed videokeratoscopy

Dry eye syndrome is one of the most commonly reported eye health conditions. Dynamic-area highspeed videokeratoscopy (DA-HSV) represents a promising alternative to the most invasive clinical methods for the assessment of the tear film surface quality (TFSQ), particularly as Placido-disk videokeratoscopy is both relatively inexpensive and widely used for corneal topography assessment. Hence, improving this technique to diagnose dry eye is of clinical significance and the aim of this work. First, a novel ray-tracing model is proposed that simulates the formation of a Placido image. This model shows the relationship between tear film topography changes and the obtained Placido image and serves as a benchmark for the assessment of indicators of the ring’s regularity. Further, a novel block-feature TFSQ indicator is proposed for detecting dry eye from a series of DA-HSV measurements. The results of the new indicator evaluated on data from a retrospective clinical study, which contains 22 normal and 12 dry eyes, have shown a substantial improvement of the proposed technique to discriminate dry eye from normal tear film subjects. The best discrimination was obtained under suppressed blinking conditions. In conclusion,this work highlights the potential of the DA-HSV as a clinical tool to diagnose dry eye syndrome.

The electronic origin of contrast reversal in bias-dependent STM images of nanolines

Self-organized Bi lines that are only 1.5 nm wide can be grown without kinks or breaks on Si(0 0 1) surfaces to lengths of up to 500 nm. Constant-current topographical images of the lines, obtained with the scanning tunneling microscope, have a striking bias dependence. Although the lines appear darker than the Si terraces at biases below ≈∣1.2∣ V, the contrast reverses at biases above ≈∣1.5∣ V. Between these two ranges the lines and terraces are of comparable brightness. It has been suggested that this bias dependence may be due to the presence of a semiconductor-like energy gap within the line. Using ab initio calculations it is demonstrated that the energy gap is too small to explain the experimentally observed bias dependence. Consequently, at this time, there is no compelling explanation for this phenomenon. An alternative explanation is proposed that arises naturally from calculations of the tunneling current, using the Tersoff–Hamann approximation, and an examination of the electronic structure of the line.

Hydrothermally formed functional niobium oxide doped tungsten nanorods

Nanorod forms of metal oxides is recognised as one of the most remarkable morphologies. Their structure and functionality have driven important advancements in a vast range of electronic devices and applications. In this work, we postulate a novel concept to explain how numerous localised surface states can be engineered into the bandgap of niobium oxide nanorods using tungsten. We discuss their contributions as local state surface charges for the modulation of a Schottky barrier height, relative dielectric constant and their respective conduction mechanisms. Their effect on the hydrogen gas molecule interactions mechanisms are also examined herein. We synthesised niobium tungsten oxide (Nb17W2O25) nanorods via a hydrothermal growth method and evaluated the Schottky barrier height, ideality factor, dielectric constant and trap energy level from the measured I-V vs temperature characteristics in the presence of air and hydrogen to show the validity of our postulations.

Premonolayer oxidation of nanostructured gold : an important factor influencing electrocatalytic activity

The study of the electrodeposition of polycrystalline gold in aqueous solution is important from the viewpoint that in electrocatalysis applications ill-defined micro- and nanostructured surfaces are often employed. In this work, the morphology of gold was controlled by the electrodeposition potential and the introduction of Pb(CH3COO)2•3H2O into the plating solution to give either smooth or nanostructured gold crystallites or large dendritic structures which have been characterized by scanning electron microscopy (SEM). The latter structures were achieved through a novel in situ galvanic replacement of lead with AuCl4−(aq) during the course of gold electrodeposition. The electrochemical behavior of electrodeposited gold in the double layer region was studied in acidic and alkaline media and related to electrocatalytic performance for the oxidation of hydrogen peroxide and methanol. It was found that electrodeposited gold is a significantly better electrocatalyst than a polished gold electrode; however, performance is highly dependent on the chosen deposition parameters. The fabrication of a deposit with highly active surface states, comparable to those achieved at severely disrupted metal surfaces through thermal and electrochemical methods, does not result in the most effective electrocatalyst. This is due to significant premonolayer oxidation that occurs in the double layer region of the electrodeposited gold. In particular, in alkaline solution, where gold usually shows the most electrocatalytic activity, these active surface states may be overoxidized and inhibit the electrocatalytic reaction. However, the activity and morphology of an electrodeposited film can be tailored whereby electrodeposited gold that exhibits nanostructure within the crystallites on the surface demonstrated enhanced electrocatalytic activity compared to smaller smooth gold crystallites and larger dendritic structures in potential regions well within the double layer region.

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.

Removal of herbicides from aqueous solutions by modified forms of montmorillonite

This investigation for the removal of agricultural pollutants, imazaquin and atrazine was conducted using montmorillonite (MMT) exchanged with organic cations through ion exchange. The study found that the adsorption of the herbicides was affected by the degree of organic cation saturations, the size of organic cations and the different natures of the herbicides. The modified clays intercalated with the larger surfactant molecules at the higher concentrations tended to enhance the adsorption of imazaquin and atrazine. In particular, the organoclays were highly efficient for the removal of imazaquin while the adsorption of atrazine was minimal due to the different hydrophobicities. Both imazaquin and atrazine were influenced by the changes of pH. The amphoteric imazaquin exists as an anion at the pH 5–7 and the anionic imazaquin was protonated to a neutral and further a cationic form when the pH is lower. The weak base, atrazine was also protonated at lower pH values. The anionic imazaquin had a strong affinity to the organoclays on the external surface as well as in the interlayer space of the MMT through electrostatic and hydrophobic interactions. In this study, the electrostatic interaction can be the primary mechanism involved during the adsorption process. This study also investigated a comparative adsorption for the imazaquin and atrazine and the lower adsorption of atrazine was enhanced and this phenomenon was due to the synergetic effect. This work highlights a potential mechanism for the removal of specific persistence herbicides from the environment.

Experimental and statistical investigation of Australian native plants for second-generation biodiesel production

This work explores the potential of Australian native plants as a source of second-generation biodiesel for internal combustion engines application. Biodiesels were evaluated from a number of non-edible oil seeds which are grow naturally in Queensland, Australia. The quality of the produced biodiesels has been investigated by several experimental and numerical methods. The research methodology and numerical model developed in this study can be used for a broad range of biodiesel feedstocks and for the future development of renewable native biodiesel in Australia.

The electronic properties of Si(001)–Bi(2 × n)

A Bi 2 × n surface net was grown on the Si(001) surface and studied with inverse photoemission, scanning tunnelling microscopy and ab initio and empirical pseudopotential calculations. The experiments demonstrated that Bi adsorption eliminates the dimer related π1* and π2* surface states, produced by correlated dimer buckling, leaving the bulk bandgap clear of unoccupied surface states. Ab initio calculations support this observation and demonstrate that the surface states derived from the formation of symmetric Bi dimers do not penetrate the fundamental bandgap of bulk Si. Since symmetric Bi dimers are an important structural component of the recently discovered Bi nanolines, that self-organize on Si(001) above the Bi desorption temperature, a connection will be made between our findings and the electronic structure of the nanolines.

The geostationary orbit : a critical legal geography of space’s most valuable real estate

This chapter attends to the legal and political geographies of one of Earth's most important, valuable, and pressured spaces: the geostationary orbit. Since the first, NASA, satellite entered it in 1964, this small, defined band of Outer Space, 35,786km from the Earth's surface, and only 30km wide, has become a highly charged legal and geopolitical environment, yet it remains a space which is curiously unheard of outside of specialist circles. For the thousands of satellites which now underpin the Earth's communication, media, and data industries and flows, the geostationary orbit is the prime position in Space. The geostationary orbit only has the physical capacity to hold approximately 1500 satellites; in 1997 there were approximately 1000. It is no overstatement to assert that media, communication, and data industries would not be what they are today if it was not for the geostationary orbit. This chapter provides a critical legal geography of the geostationary orbit, charting the topography of the debates and struggles to define and manage this highly-important space. Drawing on key legal documents such as the Outer Space Treaty and the Moon Treaty, the chapter addresses fundamental questions about the legal geography of the orbit, questions which are of growing importance as the orbit’s available satellite spaces diminish and the orbit comes under increasing pressure. Who owns the geostationary orbit? Who, and whose rules, govern what may or may not (literally) take place within it? Who decides which satellites can occupy the orbit? Is the geostationary orbit the sovereign property of the equatorial states it supertends, as these states argued in the 1970s? Or is it a part of the res communis, or common property of humanity, which currently legally characterises Outer Space? As challenges to the existing legal spatiality of the orbit from launch states, companies, and potential launch states, it is particularly critical that the current spatiality of the orbit is understood and considered. One of the busiest areas of Outer Space’s spatiality is international territorial law. Mentions of Space law tend to evoke incredulity and ‘little green men’ jokes, but as Space becomes busier and busier, international Space law is growing in complexity and importance. The chapter draws on two key fields of research: cultural geography, and critical legal geography. The chapter is framed by the cultural geographical concept of ‘spatiality’, a term which signals the multiple and dynamic nature of geographical space. As spatial theorists such as Henri Lefebvre assert, a space is never simply physical; rather, any space is always a jostling composite of material, imagined, and practiced geographies (Lefebvre 1991). The ways in which a culture perceives, represents, and legislates that space are as constitutive of its identity--its spatiality--as the physical topography of the ground itself. The second field in which this chapter is situated—critical legal geography—derives from cultural geography’s focus on the cultural construction of spatiality. In his Law, Space and the Geographies of Power (1994), Nicholas Blomley asserts that analyses of territorial law largely neglect the spatial dimension of their investigations; rather than seeing the law as a force that produces specific kinds of spaces, they tend to position space as a neutral, universally-legible entity which is neatly governed by the equally neutral 'external variable' of territorial law (28). 'In the hegemonic conception of the law,' Pue similarly argues, 'the entire world is transmuted into one vast isotropic surface' (1990: 568) on which law simply acts. But as the emerging field of critical legal geography demonstrates, law is not a neutral organiser of space, but is instead a powerful cultural technology of spatial production. Or as Delaney states, legal debates are “episodes in the social production of space” (2001, p. 494). International territorial law, in other words, makes space, and does not simply govern it. Drawing on these tenets of the field of critical legal geography, as well as on Lefebvrian concept of multipartite spatiality, this chapter does two things. First, it extends the field of critical legal geography into Space, a domain with which the field has yet to substantially engage. Second, it demonstrates that the legal spatiality of the geostationary orbit is both complex and contested, and argues that it is crucial that we understand this dynamic legal space on which the Earth’s communications systems rely.

Crowdsourcing information systems : definition, typology and design

Crowdsourcing has become a popular approach for capitalizing on the potential of large and open crowds of people external to the organization. While crowdsourcing as a phenomenon is studied in a variety of fields, research mostly focuses on isolated aspects and little is known about the integrated design of crowdsourcing efforts. We introduce a socio-technical systems perspective on crowdsourcing, which provides a deeper understanding of the components and relationships in crowdsourcing systems. By considering the function of crowdsourcing systems within their organizational context, we develop a typology of four distinct system archetypes. We analyze the characteristics of each type and derive a number of design requirements for the respective system components. The paper lays a foundation for IS-based crowdsourcing research, channels related academic work, and helps guiding the study and design of crowdsourcing information systems.