Identifying the isolated transition metal ions/oxides in molecular sieves and on oxide supports by UV resonance Raman spectroscopy

Isolated transition metal ions/oxides in molecular sieves and on surfaces are a class of active sites for selective oxidation of hydrocarbons. Identifying the active sites and their coordination structure is vital to understanding their essential role played in catalysis and designing and synthesizing more active and selective catalysts. The isolated transition metal ions in the framework of molecular sieves (e.g., TS-1, Fe-ZSM-5, and V-MCM-41) or on the surface of oxides (e.g., MoO3/Al2O3 and TiO2/SiO2) were successfully identified by UV resonance Raman spectroscopy. The charge transfer transitions between the transition metal ions and the oxygen anions are excited by a UV laser and consequently the UV resonance Raman effect greatly enhances the Raman signals of the isolated transition metal ions. The local coordination of these ions in the rigid framework of molecular sieves or in the relatively flexible structure on the surface can also be differentiated by the shifts of the resonance Raman bands. The relative concentration of the isolated transition metal ion/oxides could be estimated by the intensity ratio of Raman bands. This study demonstrates that the UV resonance Raman spectroscopy is a general technique that can be widely applied to the in-situ characterization of catalyst synthesis and catalytic reactions. (C) 2003 Elsevier Science (USA). All rights reserved.

Effect of properties of active carbon supports on performance of Pt/C catalysts in polymer electrolyte membrane fuel cell

The Pt/C catalysts were prepared with pine active carbon and Vulcan XC-72 active carbon as the supports. The performances of the Pt/C catalysts in polymer electrolyte membrane fuel cell were compared. The result indicates that the performance of Pt/Vulcan XC-72 is better than that of Pt/pine. The physical and chemical properties of the two active carbons were measured using several analysis techniques. It was found that the pore size, specific conductivity and the surface function group significantly influence the performance of the electrocatalyst.

Ammonia synthesis over Ru/C catalysts with different carbon supports promoted by barium and potassium compounds

Ammonia synthesis over ruthenium catalysts supported on different carbon materials using Ba or K compounds as promoters has been investigated. Ba(NO3)(2), KOH, and KNO3 are used as the promoter or promoter precursor, and activated carbon (AC), activated carbon fiber (ACF). and carbon molecular sieve (CMS) are used as the support. The activity measurement for ammonia synthesis was carried out in a flow micro-reactor under mild conditions: 350-450 degreesC and 3.0 MPa. Results show that KOH promoter was more effective than KNO3. and that Ba(NO3)(2) was the most effective promoter among the three. The roles of promoters can be divided into the electronic modification of ruthenium, the neutralization of surface functional groups on the carbon support and the ruthenium precursor. The catalyst with AC as the support gave the highest ammonia concentration in the effluent among the supports used, while the catalyst with ACF as the support showed the highest turnover-frequency (TOF) value. It seems that the larger particles of Ru on the carbon supports are more active for ammonia synthesis in terms of TOF value. (C) 2001 Elsevier Science B.V. All rights reserved.

Can population-level variation in early childhood development be measured in a manner that supports service planning and intervention?

Background: The Early Development Instrument (EDI) is a population-level measure of five developmental domains at school-entry age. The overall aim of this thesis was to explore the potential of the EDI as an indicator of early development in Ireland. Methods: A cross-sectional study was conducted in 47 primary schools in 2011 using the EDI and a linked parental questionnaire. EDI (teacher completed) scores were calculated for 1,344 children in their first year of full-time education. Those scoring in the lowest 10% of the sample population in one or more domains were deemed to be 'developmentally vulnerable'. Scores were correlated with contextual data from the parental questionnaire and with indicators of area and school-level deprivation. Rasch analysis was used to determine the validity of the EDI. Results: Over one quarter (27.5%) of all children in the study were developmentally vulnerable. Individual characteristics associated with increased risk of vulnerability were being male; under 5 years old; and having English as a second language. Adjusted for these demographics, low birth weight, poor parent/child interaction and mother’s lower level of education showed the most significant odds ratios for developmental vulnerability. Vulnerability did not follow the area-level deprivation gradient as measured by a composite index of material deprivation. Children considered by the teacher to be in need of assessment also had lower scores, which were not significantly different from those of children with a clinical diagnosis of special needs. all domains showed at least reasonable fit to the Rasch model supporting the validity of the instrument. However, there was a need for further refinement of the instrument in the Irish context. Conclusion: This thesis provides a unique snapshot of early development in Ireland. The EDI and linked parental questionnaires are promising indicators of the extent, distribution and determinants of developmental vulnerability.

Perceptions, expectations, and informal supports influence exercise activity in frail older adults

This study aims to explore frail older adults’ perceptions of what influences their exercise behaviors. A qualitative descriptive design was used. Semi-structured, open-ended interviews were conducted with 29 frail older adults. Thematic content analysis established the findings. Frail older adults perceive exercise as a by-product of other purposeful activities such as manual work or social activities. Progression into frailty appears to be associated with a decline in non-family support, changing traditional roles within family support networks, and lower baseline activity levels. Frail older adults perceive exercise as incidental to more purposeful activities rather than an endpoint in itself. Therefore, exercise programs concentrating on functional outcomes may be more relevant for this population. Strategies that educate and promote social support networks may also benefit frail older adults.

rbcL analysis supports the tribe Gymnothamnieae Kajimura (Ceramiaceae, Rhodophyta)

The tribe Gymnothamnieae Kajimura was proposed for the monotypic ceramiacean genus Gymnothamnion J. Agardh, previously placed either in the Ptiloteae Cramer or the Antithamnieae Hommersand. A bisporangial isolate of G. elegans (Schousboe ex C. Agardh) J. Agardh from Morocco formed only bisporangia in culture. Its smaller uninucleate cells and sporangia than those of tetrasporophytes suggested that bisporophytes may be haploid as in another member of the Ceramiaceae, Aglaothamnion diaphanum L'Hardy-Halos et Maggs. Phylogenetic analyses of the gene for the large subunit of rubisco (rbcL) from Gymnothamnion and representatives of eight other tribes of the Ceramiaceae confirmed that the removal of Gymnothamnion from the Ptiloteae and the Antithamnieae was warranted. Whereas all tribes with two or more representatives in our analyses were moderately or robustly resolved, Gymnothamnion did not form a strong clade with any other taxa. Analysis of rbcL sequences failed to resolve relationships between tribes, probably due to saturation at the high levels of sequence divergence found. In addition to reproductive features previously reported and interpreted as primitive, G. elegans shows a primitive vegetative feature and it is suggested that Gymnothamnion may be one of the most basal of the taxa presently included in the Ceramiaceae.

Preparation of nanoparticulate metal catalysts in porous supports using an ionic liquid route; hydrogenation and C-C coupling

Aerogels containing palladium metal nanoparticles were prepared using an ionic liquid route and tested for activity towards hydrogenation and Heck C-C coupling reactions. (C) 2003 Elsevier B.V. All rights reserved.

Clean preparation of nanoparticulate metals in porous supports: a supercritical route

Here we present the synthesis of nanometre sized silver particles which have been trapped within porous substrates; poly( styrene-divinylbenzene) beads and silica aerogels. This is the first time that supercritical carbon dioxide has been used to impregnate such porous materials with silver coordination complexes. In this paper we demonstrate that control over the resultant nanoparticles with respect to size, loading and distribution in the support material has been achieved by simple choice of the precursor complex. The solubility of the precursor complexes in the supercritical solvent is shown to be one of the key parameters in determining the size of the nanoparticles, their distribution and their homogeneity within the support matrix. Moreover, we demonstrate that the same methodology can be applied to two very different substrate materials. In the particular case of aerogels, conventional organic solvents could not be used to prepare nanoparticles because the surface tension of the solvent would lead to fracturing of the aerogel structure.

Capillary microreactors wall-coated with mesoporous titania thin film catalyst supports

A new method for catalyst deposition on the inner walls of capillary microreactors is proposed which allows exact control of the coating thickness, pore size of the support, metal particle size, and metal loading. The wall-coated microreactors have been tested in a selective hydrogenation reaction. Activity and selectivity reach values close to those obtained with a homogeneous Pd catalyst. The catalyst activity was stable for a period of 1000 h time-on-stream.