Remote control of the activity of a Pt catalyst supported on a mixed ionic electronic conducting membrane

A novel configuration for the in situ control of the catalytic activity of a polycrystalline Pt catalyst supported on a mixed ionic electronic conducting (MIEC) substrate is investigated. The modification of the catalytic activity is achieved by inducing the reverse spillover of oxygen promoting species from the support onto the catalyst surface, thus modifying the chemisorptive bond energy of the gas phase adsorbed reactants. This phenomenon is known as Electrochemical Promotion of Catalysis (EPOC). In this work we investigate the use of a wireless system that takes advantage of the mixed ionic electronic conductivity of the catalyst support (internally short-circuiting the system) in a dual chamber reactor. In this wireless configuration, the reaction takes place in one chamber of the membrane reactor while introduction of the promoting species is achieved by the use of an appropriate sweep gas (and therefore control of the oxygen chemical potential difference across the membrane) on the other chamber. Experimental results have shown that the catalytic rate can be enhanced by using an oxygen sweep, while a hydrogen sweep can reverse the changes. Total rate enhancement ratios of up to 3.5 were measured. © 2008 Elsevier B.V. All rights reserved.

In situ modification of a Pt catalyst supported on a mixed ionic-electronic conducting membrane

The electrochemical promotion of a platinum catalyst for ethylene oxidation on a dual chamber membrane reactor was studied. The catalyst was supported on a La_0.6Sr_0.4Co_0.2Fe_0.803 membrane. Due the supporting membrane's electronic conductivity it is possible to promote the reaction by controlling the oxygen chemical potential difference across the membrane. Upon establishment of an oxygen potential difference across the membrane, oxygen species can migrate and spillover onto the catalyst surface, modifying the catalytic activity. Initial experiments showed an overall promotion of approximately one order of magnitude of the reaction rate of ethylene, under an oxygen atmosphere on the sweep side of the membrane reactor, as compared with the rate under an inert sweep gas. The reaction rate can keep its promoted state even after the flow of oxygen on the sweep side was interrupted. This behavior caused further promotion with every experiment cycle. The causes of permanent promotion and on demonstrating controllable promotion of the catalytic activity are presented. This is an abstract of a paper presented at the AIChE Annual Meeting (San Francisco, CA 11/12-17/2006).

Electrochemical promotion of a metal catalyst supported on a mixed-ionic conductor

It has been found that the catalytic activity and selectivity of a metal film deposited on a solid electrolyte could be enhanced dramatically and in a reversible way by applying an electrical current or potential between the metal catalyst and the counter electrode (also deposited on the electrolyte). This phenomenon is know as NEMCA [S. Bebelis, C.G. Vayenas, Journal of Catalysis, 118 (1989) 125-146.] or electrochemical promotion (EP) [J. Prichard, Nature, 343 (1990) 592.] of catalysis. Yttria-doped barium zirconate, BaZr_0.9Y_0.1O_{3 - α} (BZY), a known proton conductor, has been used in this study. It has been reported that proton conducting perovskites can, under the appropriate conditions, act also as oxide ion conductors. In mixed conducting systems the mechanism of conduction depends upon the gas atmosphere that to which the material is exposed. Therefore, the use of a mixed ionic (oxide ion and proton) conducting membrane as a support for a platinum catalyst may facilitate the tuning of the promotional behaviour of the catalyst by allowing the control of the conduction mechanism of the electrolyte. The conductivity of BZY under different atmospheres was measured and the presence of oxide ion conduction under the appropriate conditions was confirmed. Moreover, kinetic experiments on ethylene oxidation corroborated the findings from the conductivity measurements showing that the use of a mixed ionic conductor allows for the tuning of the reaction rate. © 2006 Elsevier B.V. All rights reserved.

UK publicly funded Clinical Trials Units supported a controlled access approach to share individual participant data but highlighted concerns

OBJECTIVES: Evaluate current data sharing activities of UK publicly funded Clinical Trial Units (CTUs) and identify good practices and barriers.

STUDY DESIGN AND SETTING: Web-based survey of Directors of 45 UK Clinical Research Collaboration (UKCRC)-registered CTUs.

RESULTS: Twenty-three (51%) CTUs responded: Five (22%) of these had an established data sharing policy and eight (35%) specifically requested consent to use patient data beyond the scope of the original trial. Fifteen (65%) CTUs had received requests for data, and seven (30%) had made external requests for data in the previous 12 months. CTUs supported the need for increased data sharing activities although concerns were raised about patient identification, misuse of data, and financial burden. Custodianship of clinical trial data and requirements for a CTU to align its policy to their parent institutes were also raised. No CTUs supported the use of an open access model for data sharing.

CONCLUSION: There is support within the publicly funded UKCRC-registered CTUs for data sharing, but many perceived barriers remain. CTUs are currently using a variety of approaches and procedures for sharing data. This survey has informed further work, including development of guidance for publicly funded CTUs, to promote good practice and facilitate data sharing.

Selective Hydrogenation of Halogenated Arenes using porous Manganese Oxide (OMS-2) and Platinum supported OMS-2 Catalysts

Porous manganese oxide (OMS-2) and platinum supported on OMS-2 catalysts have been shown to facilitate the hydrogenation of the nitro group on chloronitrobenzene to give chloroaniline with no dehalogenation. Complete conversion was obtained within 2 h at 25 [degree]C and, although the rate of reaction increased with increasing temperature up to 100 [degree]C, the selectivity to chloroaniline remained at 99.0%. Use of Pd/OMS-2 or Pt/Al2O3 resulted in significant dechlorination even at 25 [degree]C and 2 bar hydrogen pressure giving selectivity to chloroaniline of 34.5% and 77.8%, respectively, at complete conversion. This demonstrates the potential of using platinum group metal free catalysts for the selective hydrogenation of halogenated aromatics. Two pathways were observed for the analogous nitrobenzene hydrogenation depending on the catalyst used. The hydrogenation of nitrobenzene was found to follow a direct pathway to aniline and nitrosobenzene over Pd/OMS-2 in contrast to the OMS and Pt/OMS-2 catalysts which resulted in formation of nitrosobenzene, azoxybenzene and azobenzene/hydrazobenzene intermediates before complete conversion to aniline. These results indicate that for the Pt/OMS-2 the hydrogenation proceeds predominantly over the support with the metal acting to dissociate the hydrogen. In the case of the Pd/OMS-2 both the hydrogenation and the hydrogen adsorption occur on the metal sites.

Shear behaviour of steel-fibre-reinforced concrete simply supported beams

The structural behaviour of steel-fibre-reinforced concrete beams was studied using non-linear finite-element analysis and existing experimental data. The work aim was to examine the potential of using steel fibres to reduce the amount of conventional transverse steel reinforcement without compromising ductility and strength requirements set out in design codes. To achieve this, the spacing between shear links was increased while steel fibres were added as a substitute. Parametric studies were subsequently carried out and comparisons were also made with BS EN 1992-1-1 predictions. It was concluded that the addition of steel fibres enhanced the load-carrying capacity and also altered the failure mode from a brittle shear mode to a flexural ductile one. The provision of fibres also improved ductility. However, interestingly it was found that adding excessive amounts of fibres led to a less-ductile response. Overall, the study confirmed the potential for fibres to compensate for a reduction in conventional shear reinforcement.

DPSIR framework application supported by integrated watershed modeling for irrigation from Alqueva dam (Portugal) on Guadiana river estuary

Dissertação de mest., Gestão da Água e da Costa, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2009

The Role of Teacher Presence during Computer Supported Online Collaborative Sessions in an Adult Education Course.

The convenience sample for this study was taken from an A.E.C. (Attestation of Collegial Studies) Communication course of the Continuing Education Technical Support Program. A key component of this course competency is for students to develop the skill to write business letters for various purposes and to apply the three-step writing process during the crafting of the correspondence. This is achieved with a number of writing assignments which are carried out by students working in teams and completing the writing assignments out-of-class. the out-of-class work was convened using the PrimaryPad program to complete two of the writing assignments, which formed the basis of the research. This research uses a case study design that employed a repeated measures method with two conditions (teacher scaffolding vs. no teacher scaffolding). The possibility of an order effect was controlled for by using a counterbalancing of treatment design. A post-treatment questionnaire was used to gather descriptive statistics.

Demand response programs definition supported by clustering and classification techniques

The growing importance and influence of new resources connected to the power systems has caused many changes in their operation. Environmental policies and several well know advantages have been made renewable based energy resources largely disseminated. These resources, including Distributed Generation (DG), are being connected to lower voltage levels where Demand Response (DR) must be considered too. These changes increase the complexity of the system operation due to both new operational constraints and amounts of data to be processed. Virtual Power Players (VPP) are entities able to manage these resources. Addressing these issues, this paper proposes a methodology to support VPP actions when these act as a Curtailment Service Provider (CSP) that provides DR capacity to a DR program declared by the Independent System Operator (ISO) or by the VPP itself. The amount of DR capacity that the CSP can assure is determined using data mining techniques applied to a database which is obtained for a large set of operation scenarios. The paper includes a case study based on 27,000 scenarios considering a diversity of distributed resources in a 33 bus distribution network.

Zonal prices analysis supported by a data mining based methodology

A methodology based on data mining techniques to support the analysis of zonal prices in real transmission networks is proposed in this paper. The mentioned methodology uses clustering algorithms to group the buses in typical classes that include a set of buses with similar LMP values. Two different clustering algorithms have been used to determine the LMP clusters: the two-step and K-means algorithms. In order to evaluate the quality of the partition as well as the best performance algorithm adequacy measurements indices are used. The paper includes a case study using a Locational Marginal Prices (LMP) data base from the California ISO (CAISO) in order to identify zonal prices.