Mechanistic aspects of the water–gas shift reaction on alumina-supported noble metal catalysts: In situ DRIFTS and SSITKA-mass spectrometry studies

Steady-state isotopic transient kinetic analysis (SSITKA) experiments coupled with mass spectrometry were performed for the first time to study essential mechanistic aspects of the water–gas shift (WGS) reaction over alumina-supported Pt, Pd, and Rh catalysts. In particular, the concentrations (μmol g⁻¹) of active intermediate species found in the carbon-path from CO to the CO₂ product gas (use of ¹³CO), and in the hydrogen-path from H₂O to the H₂ product gas (use of D₂O) of the reaction mechanism were determined. It was found that by increasing the reaction temperature from 350 to 500 °C the concentration of active species in both the carbon-path and hydrogen-path increased significantly. Based on the large concentration of active species present in the hydrogen-path (OH/H located on the alumina support), the latter being larger than six equivalent monolayers based on the exposed noble metal surface area (θ > 6.0), the small concentration of OH groups along the periphery of metal-support interface, and the significantly smaller concentration (μmol g⁻¹) of active species present in the carbon-path (adsorbed CO on the noble metal and COOH species on the alumina support and/or the metal-support interface), it might be suggested that diffusion of OH/H species on the alumina support towards catalytic sites present in the hydrogen-path of reaction mechanism might be considered as a slow reaction step. The formation of labile OH/H species is the result of dissociative chemisorption of water on the alumina support, where the role of noble metal is to activate the CO chemisorption and likely to promote formate decomposition into CO₂ and H₂ products. It was found that there is a good correlation between the surface concentration and binding energy of CO on the noble metal (Pt, Pd or Rh) with the activity of alumina-supported noble metal towards the WGS reaction.     

Synthesis, optical and morphological characterization of soluble main chain 1,3,4-oxadiazole copolyarylethers—potential candidates for solar cells applications as electron acceptors

New copoly(arylether)s containing substituted terphenyl, quinquephenyl, fluorene and anthracene moieties with aromatic 1,3,4-oxadiazole units were prepared and the resulting copolymers are soluble in common organic solvents. Investigation of their optical properties revealed that they emit blue and yellow light. Moreover, their photovoltaic response was studied in blends with poly(3-hexylthiophene) (P3HT) as the electron donor. Despite the low power conversion efficiencies it was shown that photo-induced electron transfer does take place and the performances are higher than a single layer P3HT device. In addition, an anthracene-fluorene-oxadiazole main chain copolymer (PAFOXD) was also examined in a single layer photovoltaic device and gave one of the highest reported open-circuit voltage (V_oc) values in the literature (0.89 V). Finally, a detailed morphological study of the blends and the PAFOXD surface using the atomic force microscopy (AFM) technique, revealed the effect of solvent selection to the preparation of thin films exhibiting the desired performance characteristics.     

Empirical evaluation of H.264/SVC streaming in resource-constrained multihomed mobile networks

Nomadic users of streamed multimedia content in mobile networks are often faced with resource-constrained network paths that suffer from low bandwidth. Streaming high-quality video in such a challenging scenario demands a set of highly adaptive schemes, which have not been sufficiently explored in particular for the emerging H.264 Scalable Video Coding (H.264/SVC) standard. In this paper, we empirically investigate the performance of streaming H.264/SVC scalable video streams to users in multihomed mobile networks containing multiple available transmission paths. Previous work has demonstrated the feasibility of aggregating bandwidth of multiple paths to deliver video streams when no single, sufficiently high bandwidth path is available. We focus on evaluating the enhanced performance of multipath bandwidth-aggregation streaming by exploiting a quality-layers based, H.264/SVC-specific packet prioritisation scheme for quality-aware multipath packet scheduling and selective packet dropping in case of bandwidth shortage even after aggregation. Additionally, we explore a base-layer rate control scheme for H.264/SVC delivery in ultra-low bandwidth environments. Through extensive experimentation on a realistic hardware-based testbed, we obtain a comprehensive and insightful understanding of the behaviour of H.264/SVC streams when transmitted across multiple paths in mobile networks. We quantify the improvements offered by the use of H.264/SVC-specific packet prioritisation schemes compared with an existing generic scalable video prioritisation scheme, and the benefits by the use of base-layer rate control in ultra-low bandwidth situations. The performance of the multipath streaming schemes is further compared with that of an ideal single high bandwidth path. We also identify the remaining challenges that must be overcome if such streaming schemes are to offer performance close to that of the ideal single high bandwidth path.     

Transitive node similarity: predicting and recommending links in signed social networks

Online social networks (OSNs) like Facebook, Myspace, and Hi5 have become popular, because they allow users to easily share content. OSNs recommend new friends to registered users based on local features of the graph (i.e., based on the number of common friends that two users share). However, OSNs do not exploit the whole structure of the network. Instead, they consider only pathways of maximum length 2 between a user and his candidate friends. On the other hand, there are global approaches, which detect the overall path structure in a network, being computationally prohibitive for huge-size social networks. In this paper, we define a basic node similarity measure that captures effectively local graph features (i.e., by measuring proximity between nodes). We exploit global graph features (i.e., by weighting paths that connect two nodes) introducing transitive node similarity. We also derive variants of our method that apply to different types of networks (directed/undirected and signed/unsigned). We perform extensive experimental comparison of the proposed method against existing recommendation algorithms using synthetic and real data sets (Facebook, Hi5 and Epinions). Our experimental results show that our FriendTNS algorithm outperforms other approaches in terms of accuracy and it is also time efficient. Finally, we show that a significant accuracy improvement can be gained by using information about both positive and negative edges.     

An empirical investigation of Technology Readiness among medical staff based in Greek hospitals

Technology readiness (TR) represents an individual’s mental readiness to accept new technologies. Although the TR scale has been used in many studies, its application in the healthcare context is limited. This paper focuses on identifying the TR profiles of medical staff and to model preference TR variations with respect to computer use, computer knowledge and computer feature demands. The study reports results from a nationwide study conducted in Greece, during a three-year period, which sampled responses from 604 physicians and nurses working in 14 Greek hospitals. Exploratory Structural Equation Modelling analysis is used in order to confirm the structure of the Technology Readiness Index. The results confirm the five groups of the TR taxonomy. Statistical differences were found between classes in information and communication technology (ICT) knowledge, ICT feature demands, hours of use per week as well as ICT use performance, but not in the general use of ICT. The results facilitate comprehension of the factors, which influence the use of ICT by medical staff and, in addition, they convey important policy and managerial implications. In conclusion, medical staff should be treated according to its TR taxonomy classes in order to expedite the acceptance and use of an ICT system.     

ON THE CHEMICAL OSCILLATIONS IN DIFFERENTIAL REACTORS: A CASE STUDY OF AMMONIA OXIDATION ON PLATINUM

Trying to identify the mechanism(s) responsible for isothermal oscillatory behavior of heterogeneous catalytic reaction systems, many investigators have assumed low conversions with respect to the limiting reactant(s) so that the bulk phase concentrations of the reactants may be considered constant. In this study, it is shown that even in a differential catalytic CSTR, in which conversion of the reactants may be less than %, the changes of the gas phase concentrations of the reacting.species may play a key role in the overall dynamic behavior of a reaction system; for instance, they may drive the oscillations observed. The reduction of nitric oxide by ammonia on polycrystalline platinum is discussed in detail within this context. Several other oxidation reactions are also discussed     

Parallel and scalable processing of spatio-temporal RDF queries using Spark

The ever-increasing size of data emanating from mobile devices and sensors, dictates the use of distributed systems for storing and querying these data. Typically, such data sources provide some spatio-temporal information, alongside other useful data. The RDF data model can be used to interlink and exchange data originating from heterogeneous sources in a uniform manner. For example, consider the case where vessels report their spatio-temporal position, on a regular basis, by using various surveillance systems. In this scenario, a user might be interested to know which vessels were moving in a specific area for a given temporal range. In this paper, we address the problem of efficiently storing and querying spatio-temporal RDF data in parallel. We specifically study the case of SPARQL queries with spatio-temporal constraints, by proposing the DiStRDF system, which is comprised of a Storage and a Processing Layer. The DiStRDF Storage Layer is responsible for efficiently storing large amount of historical spatio-temporal RDF data of moving objects. On top of it, we devise our DiStRDF Processing Layer, which parses a SPARQL query and produces corresponding logical and physical execution plans. We use Spark, a well-known distributed in-memory processing framework, as the underlying processing engine. Our experimental evaluation, on real data from both aviation and maritime domains, demonstrates the efficiency of our DiStRDF system, when using various spatio-temporal range constraints.

     

A general framework and optimization models for the scheduling of continuous chemical processes

We present a framework for the formulation and solution of continuous process scheduling problems. We focus on modeling transient operations such as startups, shutdowns, and transitions between steady states. First, we show how the concept of processing tasks can be generalized to represent continuous processes, including their transient operations. Second, we discuss how to systematically calculate the parameters describing material consumption/production and utility consumption during transient operations. Finally, we present new mixed-integer linear programming formulations for the scheduling of continuous chemical production.     

Superparamagnetic polyvinylpyrrolidone/chitosan/Fe3O4 electrospun nanofibers as effective U(VI) adsorbents

Magnetoactive electrospun fibrous membranes consisting of polyvinylpyrrolidone (PVP), chitosan (CS) and pre-fabricated, double-layer oleic acid-coated magnetite nanoparticles (OA.OA.Fe₃O₄) were fabricated and evaluated as new adsorbent materials for the removal and recovery of uranium (U(VI)) from aqueous solutions. The adsorption has been investigated by batch-type experiments and the solid material has been characterized by X-ray diffraction spectroscopy (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy/energy dispersive X-ray analysis (TEM/EDX) and vibration sample magnetometry (VSM) measurements prior and after uranium adsorption. The experimental adsorption data were found to be well fitted with the Langmuir isotherm and the pseudo-second order kinetic model. The results indicate that PVP/CS/OA.OA.Fe₃O₄ fibrous adsorbents exhibit good adsorption properties towards U(VI) in aqueous solutions, achieving a q_max value of 0.77 mol kg⁻¹ (183.3 mg g⁻¹) at pH 6.0. The experiments regarding the regeneration and reuse of the magnetoactive adsorbents were carried out using Na₂CO₃, at pH ~11. After four cycles, the percentage relative adsorption remained stable (~100%) whereas the desorption percentage decreased from 31.9% to 21.0%. Generally, the presented results demonstrate that the incorporation of the Fe₃O₄ NPs has a positive effect on the adsorption efficiency of U(VI) from aquatic environments.     

Enforcing Efficient Equilibria in Network Design Games via Subsidies

The efficient design of networks has been an important engineering task that involves challenging combinatorial optimization problems. Typically, a network designer has to select among several alternatives which links to establish so that the resulting network satisfies a given set of connectivity requirements and the cost of establishing the network links is as low as possible. The Minimum Spanning Tree problem, which is well-understood, is a nice example.In this paper, we consider the natural scenario in which the connectivity requirements are posed by selfish users who have agreed to share the cost of the network to be established according to a well-defined rule. The design proposed by the network designer should now be consistent not only with the connectivity requirements but also with the selfishness of the users. Essentially, the users are players in a so-called network design game and the network designer has to propose a design that is an equilibrium for this game. As it is usually the case when selfishness comes into play, such equilibria may be suboptimal. In this paper, we consider the following question: can the network designer enforce particular designs as equilibria or guarantee that efficient designs are consistent with users’ selfishness by appropriately subsidizing some of the network links? In an attempt to understand this question, we formulate corresponding optimization problems and present positive and negative results.