CO oxidation on Pt(111):An ab initio density functional theory study

CO oxidation on Pt(111) is studied with ab initio density functional theory. The low energy pathway and transition state for the reaction are identified. The key event is the breaking of an O-metal bond prior to the formation of a chemisorbed CO2 molecule. The pathway can be rationalized in terms of competition of the O and C atoms for bonding with the underlying surface, and the predominant energetic barrier is the strength of the O-metal bond.

Mobile Wearable Communications

This special issue provides the latest research and development on wireless mobile wearable communications. According to a report by Juniper Research, the market value of connected wearable devices is expected to reach $1.5 billion by 2014, and the shipment of wearable devices may reach 70 million by 2017. Good examples of wearable devices are the prominent Google Glass and Microsoft HoloLens. As wearable technology is rapidly penetrating our daily life, mobile wearable communication is becoming a new communication paradigm. Mobile wearable device communications create new challenges compared to ordinary sensor networks and short-range communication. In mobile wearable communications, devices communicate with each other in a peer-to-peer fashion or client-server fashion and also communicate with aggregation points (e.g., smartphones, tablets, and gateway nodes). Wearable devices are expected to integrate multiple radio technologies for various applications' needs with small power consumption and low transmission delays. These devices can hence collect, interpret, transmit, and exchange data among supporting components, other wearable devices, and the Internet. Such data are not limited to people's personal biomedical information but also include human-centric social and contextual data. The success of mobile wearable technology depends on communication and networking architectures that support efficient and secure end-to-end information flows. A key design consideration of future wearable devices is the ability to ubiquitously connect to smartphones or the Internet with very low energy consumption. Radio propagation and, accordingly, channel models are also different from those in other existing wireless technologies. A huge number of connected wearable devices require novel big data processing algorithms, efficient storage solutions, cloud-assisted infrastructures, and spectrum-efficient communications technologies.

BUCKLED LAYER STRUCTURE FOR ATOMIC ADSORPTION ON W(100) - THE (ROOT-2X-ROOT-2)R45-DEGREES NITROGEN STRUCTURE FROM ATLEED

Adsorption of 0.5 monolayer of N adatoms on W{100} results in a sharp (root 2 X root 2)R45 degrees LEED pattern. The only previous quantitative LEED study of this system gave a simple overlayer model with a Pendry R-factor of 0.55. An exhaustive search has been made of possible structures, including a novel vacancy reconstruction, displacive reconstructions and underlayer adsorption. From this work a new overlayer structure is derived with an R(p) value of 0.22, displaying a considerable buckling of 0.27 +/- 0.05 Angstrom within the second W layer and consequently involving large changes in the interlayer spacings of the surface. The N adatom is pseudo-five-fold coordinated to the W surface, bonding to a second-layer W atom with a nearest-neighbour bond length of 2.13 Angstrom and with the four next-nearest-neighbour W atoms in the surface plane at 2.27 Angstrom. The structure does not resolve the work function anomaly observed on this surface.

CLUSTER LEED - A VERY FAST METHOD FOR SURFACE-STRUCTURE DETERMINATION

A very fast method, cluster low-energy electron diffraction (LEED) is proposed for LEED I-V spectral analysis, in which three appproximations are introduced: the small-atom approximation, omission of the structure factors, and truncation of higher order ( > 2) scattering events. The method has been tested using a total of four sets of I-V spectra calculated by fully dynamic LEED for (i) the simple overlayer system, O on Ni{100}, and (ii) the reconstructed system, Cu on W{100}, and also one set of experimental data from W{100}-c(2 X 2)-Cu. In each case the correct structural parameters are recovered. It is suggested that for complex systems cluster LEED provides an efficient fast route to trial structures, which could be refined by automated tenser LEED.

A DIRECT INVERSION METHOD FOR SURFACE-STRUCTURE DETERMINATION FROM LEED INTENSITIES

LOW-ENERGY electron diffraction (LEED) has become the most successful technique in surface crystallography1, but because of the complexity of the surface-electron scattering interactions, analyses of LEED data are still conducted on a trial-and-error basis: a direct-inversion method for treating LEED intensity data remains an attractive goal2. Building on recent theoretical and experimental developments in electron holography from surface structures3-16, we show here that three-dimensional images with atomic resolution can be obtained by a direct transform of conventional LEED intensity spectra.

THE SURFACE-STRUCTURE OF A C(2 X-2) POTASSIUM OVERLAYER ON CO(1010)

The surface structure of the clean Co{1010BAR} surface and a c(2 x 2) potassium overlayer have been determined by quantitative low energy electron diffraction. The Co{1010BAR} sample has been shown to be laterally unreconstructed with the surface being uniquely terminated by an outermost closely packed double layer (dz12 = 0.68 angstrom). A damped oscillatory relaxation of the outermost three atomic layers occurs, with relaxations DELTA-dz12 = -6.5 +/- 2% and DELTA-dz23 = +1.0 +/- 2%.

The c(2 x 2) overlayer formed at a coverage of 0.5 ML was subjected to a full I-V analysis. A range of adsorption sites were tested including fourfold hollow, on-top, and both long and short bridge sites in combination with both "long" and "short" cobalt interlayer terminations. A clear preference was found for adsorption in the maximal coordination fourfold hollow site. No switching of surface termination occurs. The potassium adatoms reside in the [1210BAR] surface channels directly above second layer cobalt atoms with a potassium to outermost cobalt interlayer separation of 2.44 +/- 0.05 angstrom. Potassium-cobalt bond lengths of 3.40 +/- 0.05 and 3.12 +/- 0.05 angstrom between the four (one) outermost (second) layer nearest-neighbour substrate atoms suggests a potassium effective radius of 1.87 +/- 0.05 angstrom, somewhat smaller than the Pauling covalent radius and considerably larger than the ionic radius (1.38 angstrom). The alkali-surface bonding is thus predominantly "covalent"/"metallic".

Photocatalytic degradation of eleven microcystin analogues and nodularin by TiO2 coated glass microspheres

Microcystins and nodularin are toxic cyanobacterial secondary metabolites produced by cyanobacteria that pose a threat to human health in drinking water. Conventional water treatment methods often fail to remove these toxins. Advanced oxidation processes such as TiO2 photocatalysis have been shown to effectively degrade these compounds. A particular issue that has limited the widespread application of TiO2 photocatalysis for water treatment has been the separation of the nanoparticulate power from the treated water. A novel catalyst format, TiO2 coated hollow glass spheres (Photospheres™), is far more easily separated from treated water due to its buoyancy. This paper reports the photocatalytic degradation of eleven microcystin variants and nodularin in water using Photospheres™. It was found that the Photospheres™ successfully decomposed all compounds in 5 minutes or less. This was found to be comparable to the rate of degradation observed using a Degussa P25 material, which has been previously reported to be the most efficient TiO2 for photocatalytic degradation of microcystins in water. Furthermore, it was observed that the degree of initial catalyst adsorption of the cyanotoxins depended on the amino acid in the variable positions of the microcystin molecule. The fastest degradation (2 minutes) was observed for the hydrophobic variants (microcystin-LY, -LW, -LF). Suitability of UV-LEDs as an alternative low energy light source was also evaluated.

CO2 capture and electrochemical conversion using superbasic [P66614][124Triz]

The ionic liquid trihexyltetradecylphosphonium 1,2,4-triazolide, [P66614][124Triz], has been shown to chemisorb CO2 through equimolar binding of the carbon dioxide with the 1,2,4-triazolide anion. This leads to a possible new, low energy pathway for the electrochemical reduction of carbon dioxide to formate and syngas at low overpotentials, utilizing this reactive ionic liquid media. Herein, an electrochemical investigation of water and carbon dioxide addition to the [P66614][124Triz] on gold and platinum working electrodes is reported. Electrolysis measurements have been performed using CO2 saturated [P66614][124Triz] based solutions at −0.9 V and −1.9 V on gold and platinum electrodes. The effects of the electrode material on the formation of formate and syngas using these solutions are presented and discussed.

Temporal Narrowing of Neutrons Produced by High-Intensity Short-Pulse Lasers

The production of neutron beams having short temporal duration is studied using ultraintense laser pulses. Laser-accelerated protons are spectrally filtered using a laser-triggered microlens to produce a short duration neutron pulse via nuclear reactions induced in a converter material (LiF). This produces a similar to 3 ns duration neutron pulse with 10(4) n/MeV/sr/shot at 0.56 m from the laser-irradiated proton source. The large spatial separation between the neutron production and the proton source allows for shielding from the copious and undesirable radiation resulting from the laser-plasma interaction. This neutron pulse compares favorably to the duration of conventional accelerator sources and should scale up with, present and future, higher energy laser facilities to produce brighter and shorter neutron beams for ultrafast probing of dense materials.

New suburbia: designing in urban resilience by closing resource cycles

By utilising a research by design methodology, the paper develops a process-based and phased design to develop a new emergent form to these neighbourhoods, one in which new productive systems are embedded into the city, at a small-scales. These include a peak-load hydro-electric project in Ligoneal; a productive landscape in Glen Cairn and a city-wide energy refurbishment utilising neighbourhood waste streams.

The three projects illustrate different ways in which place-based solutions can enact urban transformation through a process of rigorous visualisation of process, and its attendant changes in content and form of the neighbourhood, These designs, based around a process-based strategy plan, allow for a roadmap for development to be created that could change the modus operandi of an area over a relatively short period of time,. The paper demonstrates that even modest investments of productive technologies at a local scale can fundamentally change the form and the economic and environmental operation of the city in the future, and create a new resilient city, one that can have resilience built-in. This resilience allows the neighbourhood to be less externally dependent on resources, economically active and more socially just.

Irradiation of bioresorbable biomaterials for controlled surface degradation

Bioresorbable polymers increasingly are the materials of choice for implantable orthopaedic fixation devices. Controlled degradation of these polymers is vital for preservation of mechanical properties during tissue repair and controlled release of incorporated agents such as osteoconductive or anti-microbial additives. The work outlined in this paper investigates the use of low energy electron beam irradiation to surface modify polyhydroxyacid samples incorporating beta tricalcium phosphate (β-TCP). This work uniquely demonstrates that surface modification of bioresorbable polymers through electron beam irradiation allows for the early release of incorporated agents such as bioactive additives. Samples were e-beam irradiated at an energy of 125 keV and doses of either 150 kGy or 500 kGy. Irradiated and non-irradiated samples were degraded in phosphate buffered saline (PBS), to simulate bioresorption, followed by characterisation. The results show that low energy e-beam irradiation enhances surface hydrolytic degradation in comparison to bulk and furthermore allows for earlier release of incorporated calcium via dissolution into the surrounding medium.

Performance of sustainable SCC mixes with mineral additions for use in precast concrete industry

The aim of this research was to study the impact that different mineral powders have on the properties of self-compacting concrete (SCC) in order to obtain relations that make it possible to optimize their dosages for being used in precast concrete applications. Different combinations and contents of cement, mineral additions (active and inert), superplasticizers, and aggregates are considered. A new approach for determining the saturation point of superplasticizers is introduced. The fresh state performance was assessed by means of the following tests: slump flow, V-funnel, and J-ring. Concrete compressive strength values at different ages up to 56 days have been retained as representative of the materials’ performance in its hardened state. All these properties have been correlated with SCC proportioning. As a result, a number of recommendations for the precast concrete industry arise to design more stable SCC mixes with a reduced carbon footprint.

Assessment of the double-skin façade passive thermal buffer effect.

Double Skin Façades (DSFs) are becoming increasingly popular architecture for commercial office buildings. Although DSFs are widely accepted to have the capacity to offer significant passive benefits and enable low energy building performance, there remains a paucity of knowledge with regard to their operation. Identification of the most determinant architectural parameters of DSFs is the focus of ongoing research. This paper presents an experimental and simulation study of a DSF installed on a commercial building in Dublin, Ireland. The DSF is south facing and acts to buffer the building from winter heat losses, but risks enhancing over-heating on sunny days. The façade is extensively monitored during winter months. Computational Fluid Dynamic (CFD) models are used to simulate the convective operation of the DSF. This research concludes DSFs as suited for passive, low energy architecture in temperature climates such as Ireland but identifies issues requiring attention in DSF design.

Experimental investigation of thermal inertia properties in hemp-lime concrete walls

Hemp-lime concrete is a sustainable alternative to standard building wall materials, with low associated embodied energy. It exhibits good hygric, acoustic and thermal properties, making it an exciting, sustainable building envelope material. When cast in temporary shuttering around a timber frame, it exhibits lower thermal conductivity than concrete, and consequently achieves low U-values in a primarily mono-material wall construction. Although cast relatively thick hemp-lime walls do not generally achieve the low U-values stipulated in building regulations. However assessment of its thermal performance through evaluation of its resistance to thermal transfer alone, underestimates its true thermal quality. The thermal inertia, or reluctance of the wall to change its temperature when exposed to changing environmental temperatures, also has a significant impact on the thermal quality of the wall, the thermal comfort of the interior space and energy consumption due to space heating. With a focus on energy reduction in buildings, regulations emphasise thermal resistance to heat transfer with only less focus on thermal inertia or storage benefits due to thermal mass. This paper investigates dynamic thermal responsiveness in hemp-lime concrete walls. It reports the influence of thermal conductivity, density and specific heat through analysis of steady state and transient heat transfer, in the walls. A novel hot-box design which isolates the conductive heat flow is used, and compared with tests in standard hot-boxes. Thermal diffusivity and effusivity are evaluated, using experimentally measured conductivity, based on analytical relationships. Experimental results evident that hemp-lime exhibits high thermal inertia. They show the thermal inertia characteristics compensate for any limitations in the thermal resistance of the construction material. When viewed together the thermal resistance and mass characteristics of hemp-lime are appropriate to maintain comfortable thermal indoor conditions and low energy operation.

Fractionated Radiation Exposure of Rat Spinal Cords Leads to Latent Neuro- Inflammation in Brain, Cognitive Deficits,and Alterations in Apurinic Endonuclease 1

Ionizing radiation causes degeneration of myelin, the insulating sheaths of neuronal axons, leading to neurological impairment. As radiation research on the central nervous system has predominantly focused on neurons, with few studies addressing the role of glial cells, we have focused our present research on identifying the latent effects of single/ fractionated -low dose of low/ high energy radiation on the role of base excision repair protein Apurinic Endonuclease-1, in the rat spinal cords oligodendrocyte progenitor cells’ differentiation. Apurinic endonuclease-1 is predominantly upregulated in response to oxidative stress by low- energy radiation, and previous studies show significant induction of Apurinic Endonuclease-1 in neurons and astrocytes. Our studies show for the first time, that fractionation of protons cause latent damage to spinal cord architecture while fractionation of HZE (28Si) induce increase in APE1 with single dose, which then decreased with fractionation. The oligodendrocyte progenitor cells differentiation was skewed with increase in immature oligodendrocytes and astrocytes, which likely cause the observed decrease in white matter, increased neuro-inflammation, together leading to the observed significant cognitive defects.