Dependence of Gas-Phase Crotonaldehyde Hydrogenation Selectivity and Activity on the Size of Pt Nanoparticles (1.7-7.1 nm) Supported on SBA-15

The selectivity and activity for the hydrogenation of crotonaldehyde to crotyl alcohol and butyraldehyde was studied over a series of Pt nanoparticles (diameter of 1.7, 2.9, 3.6, and 7.1 nm). The nanoparticles were synthesized by the reduction of chloroplatinic acid by alcohol in the presence of poly(vinylpyrrolidone) (PVP), followed by encapsulation into mesoporous SBA-15 silica. The rate of crotonaldehyde hydrogenation and selectivity towards crotyl alcohol both increase with increasing particle size. The selectivity towards crotyl alcohol increased from 13.7 % to 33.9 % (8 Torr crotonaldehyde, 160 Torr H{sub 2} and 353 K), while the turnover frequency increases from 2.1 x 10{sup -2} s{sup -1} to 4.8 x 10{sup -2} s{sup -1} with an increase in the particle size from 1.7 nm to 7.1 nm. The decarbonylation pathway to form propene and CO is enhanced over the higher proportion of coordinatively unsaturated sites on the smaller nanoparticles. The apparent activation energy remains constant ({approx} 16 kcal mol{sup -1} for the formation of butyraldehyde and {approx} 8 kcal mol{sup -1} for the formation of crotyl alcohol) as a function of particle size. In the presence of 130-260 mTorr CO, the reaction rate decreases for all products with a CO reaction order of -0.9 for crotyl alcohol and butyraldehyde over 7.1 nm Pt particles; over 1.7 nm Pt particles, the order in CO is -1.4 and -0.9, respectively. Hydrogen reduction at 673 K after calcination in oxygen results in increased activity and selectivity relative to reduction at either higher or lower temperature; this is discussed with regards to the incomplete removal and/or change in morphology of the polymeric surface stabilizing agent, poly(vinylpyrrolidone) used for the synthesis of the Pt nanoparticles

Favoriser les relocalisations industrielles au Québec par le biais des politiques publiques II : le Québec est-il mûr pour une réindustrialisation d’ampleur? Un aperçu de l’état du secteur manufacturier québécois

La réindustrialisation, notamment par l’entremise des relocalisations et dont la substitution des importations est l’un des effets directs, représente une tendance lourde des stratégies économiques occidentales depuis la crise financière de 2008, qui a mis en évidence les dangers de la financiarisation, de la stagnation des investissements productifs, des délocalisations industrielles et de la déconnexion entre les politiques publiques et l’économie « réelle ». Le Québec ne fait pas exception à cette règle, bien que la croissance annuelle moyenne de son PIB manufacturier depuis cette crise (environ 1,4%) ait été assez substantiellement inférieure à celle des principales puissances industrielles occidentales. Cette croissance du secteur manufacturier depuis 2009 n’a pu que ralentir son déclin relatif en proportion du PIB québécois, son poids stagnant autour des 14% depuis une dizaine d’années alors qu’il atteignait encore les 20% au tournant des années 2000. Dans un rapport détaillé publié simultanément à la présente note et auquel nous invitons les lecteurs intéressés et avertis à se référer, l’IRÉC établit dans quelle mesure et de quelles manières, dans un objectif de relocalisation partielle de ses chaînes de valeur manufacturières, le Québec peut envisager à moyen et long termes une réindustrialisation d’ampleur

Survey of Materials for Nanoskiving and Influence of the Cutting Process on the Nanostructures Produced

This paper examines the factors that influence the quality of nanostructures fabricated by sectioning thin films with an ultramicrotome (“nanoskiving”). It surveys different materials (metals, ceramics, semiconductors, and conjugated polymers), deposition techniques (evaporation, sputter deposition, electroless deposition, chemical-vapor deposition, solution-phase synthesis, and spin-coating), and geometries (nanowires or two-dimensional arrays of rings and crescents). It then correlates the extent of fragmentation of the nanostructures with the composition of the thin films, the methods used to deposit them, and the parameters used for sectioning. There are four major conclusions. (i) Films of soft and compliant metals (those that have bulk values of hardness less than or equal to those of palladium, or ≤500 MPa) tend to remain intact upon sectioning, whereas hard and stiff metals (those that have values of hardness greater than or equal to those of platinum, or ≥500 MPa) tend to fragment. (ii) All conjugated polymers tested form intact nanostructures. (iii) The extent of fragmentation is lowest when the direction of cutting is perpendicular to the exposed edge of the embedded film. (iv) The speed of cutting−from 0.1 to 8 mm/s−has no effect on the frequency of defects. Defects generated during sectioning include scoring from defects in the knife, delamination of the film from the matrix, and compression of the matrix. The materials tested were: aluminum, titanium, nickel, copper, palladium, silver, platinum, gold, lead, bismuth, germanium, silicon dioxide ($\textrm{SiO}_2$), alumina ($\textrm{Al}_2\textrm{O}_3$), tin-doped indium oxide (ITO), lead sulfide nanocrystals, the semiconducting polymers poly(2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene) (MEH-PPV), poly(3-hexylthiophene) (P3HT), and poly(benzimidazobenzophenanthroline ladder) (BBL), and the conductive polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS).Chemistry and Chemical Biolog

Diffusion doping of cobalt in rod-shape anatase TiO\u3csub\u3e2\u3c/sub\u3e nanocrystals leads to antiferromagnetism†

Cobalt(II) ions were adsorbed to the surface of rod-shape anatase TiO2 nanocrystals and subsequently heated to promote ion diffusion into the nanocrystal. After removal of any remaining surface bound cobalt, a sample consisting of strictly cobalt-doped TiO2 was obtained and characterized with powder Xray diffraction, transmission electron microscopy, UV-visible spectroscopy, fluorescence spectroscopy, X-ray photoelectron spectroscopy, SQUID magnetometry, and inductively-coupled plasma atomic emission spectroscopy. The nanocrystal morphology was unchanged in the process and no new crystal phases were detected. The concentration of cobalt in the doped samples linearly correlates with the initial loading of cobalt(II) ions on the nanocrystal surface. Thin films of the cobalt doped TiO2 nanocrystals were prepared on indium-tin oxide coated glass substrate, and the electrical conductivity increased with the concentration of doped cobalt. Magnetic measurements of the cobalt-doped TiO2 nanocrystals reveal paramagnetic behavior at room temperature, and antiferromagnetic interactions between Co ions at low temperatures. Antiferromagnetism is atypical for cobalt-doped TiO2 nanocrystals, and is proposed to arise from interstitial doping that may be favored by the diffusional doping mechanism

Effects of chloride ions in acid-catalyzed biomass dehydration reactions in polar aprotic solvents

The use of polar aprotic solvents in acid-catalyzed biomass conversion reactions can lead to improved reaction rates and selectivities. We show that further increases in catalyst performance in polar aprotic solvents can be achieved through the addition of inorganic salts, specifically chlorides. Reaction kinetics studies of the Brønsted acid-catalyzed dehydration of fructose to hydroxymethylfurfural (HMF) show that the use of catalytic concentrations of chloride salts leads to a 10-fold increase in reactivity. Furthermore, increased HMF yields can be achieved using polar aprotic solvents mixed with chlorides. Ab initio molecular dynamics simulations (AIMD) show that highly localized negative charge on Cl− allows the chloride anion to more readily approach and stabilize the oxocarbenium ion that forms and the deprotonation transition state. High concentrations of polar aprotic solvents form local hydrophilic environments near the reactive hydroxyl group which stabilize both the proton and chloride anions and promote the dehydration of fructose

Evaluating Differences in the Active-Site Electronics of Supported Au Nanoparticle Catalysts Using Hammett and DFT Studies

Supported metal catalysts, which are composed of metal nanoparticles dispersed on metal oxides or other high-surface-area materials, are ubiquitous in industrially catalysed reactions. Identifying and characterizing the catalytic active sites on these materials still remains a substantial challenge, even though it is required to guide rational design of practical heterogeneous catalysts. Metal-support interactions have an enormous impact on the chemistry of the catalytic active site and can determine the optimum support for a reaction; however, few direct probes of these interactions are available. Here we show how benzyl alcohol oxidation Hammett studies can be used to characterize differences in the catalytic activity of Au nanoparticles hosted on various metal-oxide supports. We combine reactivity analysis with density functional theory calculations to demonstrate that the slope of experimental Hammett plots is affected by electron donation from the underlying oxide support to the Au particles

Development of a MSW gasification model for flexible integration into a MFA-LCA framework

This paper presents the development of a comprehensive gasification module designed to be integrated in a MFA-LCA framework. From existing gasification models present in the literature, the most appropriate modelling strategy is selected and implemented into the module. This module needs to be able to capture the influence of input parameters, such as gasification reactor type, oxidizing agent, feedstock composition and operating conditions on the process outputs, including syngas yield, its composition and LHV, as well as tar and char contents. A typical gasification process is usually modelled in four steps: drying, pyrolysis, oxidation and reduction. Models representing each of these steps are presented in this paper. Since the type of gasification reactor is taken into account in the module, models for downdraft moving bed and bubbling fluidized bed reactor are also reviewed. The gasification module will be integrated into a MFA framework (VMR-Sys), which enables calculation of relevant gasifier feedstock parameters, such as moisture content, composition, properties and particle size distribution. Outputs from the module will also include elemental compositions obtained from VMR-Sys calculations. Finally, all outputs from the module will be used to build LCA-inventory data

Lessons learned from 104 years of mobile observatories [poster]

Poster session IN13B-1211 presented 10 December 2007 at the AGU Fall Meeting, 10–14 December 2007, San Francisco, CA, USAAs the oceanographic community ventures into a new era of integrated observatories, it may be helpful to look back on the era of "mobile observatories" to see what Cyberinfrastructure lessons might be learned. For example, SIO has been operating research vessels for 104 years, supporting a wide range of disciplines: marine geology and geophysics, physical oceanography, geochemistry, biology, seismology, ecology, fisheries, and acoustics. In the last 6 years progress has been made with diverse data types, formats and media, resulting in a fully-searchable online SIOExplorer Digital Library of more than 800 cruises (http://SIOExplorer.ucsd.edu). Public access to SIOExplorer is considerable, with 795,351 files (206 GB) downloaded last year. During the last 3 years the efforts have been extended to WHOI, with a "Multi-Institution Testbed for Scalable Digital Archiving" funded by the Library of Congress and NSF (IIS 0455998). The project has created a prototype digital library of data from both institutions, including cruises, Alvin submersible dives, and ROVs. In the process, the team encountered technical and cultural issues that will be facing the observatory community in the near future. Technological Lessons Learned: Shipboard data from multiple institutions are extraordinarily diverse, and provide a good training ground for observatories. Data are gathered from a wide range of authorities, laboratories, servers and media, with little documentation. Conflicting versions exist, generated by alternative processes. Domain- and institution-specific issues were addressed during initial staging. Data files were categorized and metadata harvested with automated procedures. With our second-generation approach to staging, we achieve higher levels of automation with greater use of controlled vocabularies. Database and XML- based procedures deal with the diversity of raw metadata values and map them to agreed-upon standard values, in collaboration with the Marine Metadata Interoperability (MMI) community. All objects are tagged with an expert level, thus serving an educational audience, as well as research users. After staging, publication into the digital library is completely automated. The technical challenges have been largely overcome, thanks to a scalable, federated digital library architecture from the San Diego Supercomputer Center, implemented at SIO, WHOI and other sites. The metadata design is flexible, supporting modular blocks of metadata tailored to the needs of instruments, samples, documents, derived products, cruises or dives, as appropriate. Controlled metadata vocabularies, with content and definitions negotiated by all parties, are critical. Metadata may be mapped to required external standards and formats, as needed. Cultural Lessons Learned: The cultural challenges have been more formidable than expected. They became most apparent during attempts to categorize and stage digital data objects across two institutions, each with their own naming conventions and practices, generally undocumented, and evolving across decades. Whether the questions concerned data ownership, collection techniques, data diversity or institutional practices, the solution involved a joint discussion with scientists, data managers, technicians and archivists, working together. Because metadata discussions go on endlessly, significant benefit comes from dictionaries with definitions of all community-authorized metadata values.Funding provided by the Library of Congress and NSF (IIS 0455998