Les piles à combustibles permettent de convertir l'énergie chimique en énergie électrique. Il existe différents types de piles; les mieux adaptées pour équiper un véhicule électrique étant actuellement les PEM (Proton Exchange Membrane). Elles nécessitent une alimentation en hydrogène pur, pouvant provenir du réformage in situ de carburants. Les produits du réformage sont constitués d'un mélange de gaz dont il faut extraire l'hydrogène pour alimenter la pile. Pour séparer les composants d'un mélange gazeux, un moyen simple consiste à utiliser une membrane de perméation. Le palladium étant perméable sélectivement à l'hydrogène, il est le matériau de choix pour la réalisation de membranes de purification de l'hydrogène. Ce travail a consisté à élaborer cette membrane en déposant un film fin de palladium sur un support mécanique poreux. La technique utilisée est celle de l'électroless: un sel de palladium et un réducteur sont mis en présence et le dépôt se fait sur la surface catalytique du substrat. Le travail bibliographique sur cette technique est suivi d'études expérimentales sur support dense afin de comprendre les différents facteurs gouvernant ce dépôt. Dans un premier temps, des mesures potentiométriques ont été réalisées afin de déterminer l'influence de divers facteurs sur le potentiel électrochimique du bain. Puis, des cinétiques de prise de masse du substrat ont été enregistrées afin de faire le lien entre les conditions opératoires et le rendement de dépôt obtenu ainsi que son adhérence au substrat. Ensuite, le! s dépôts de palladium ont été testés sur des substrats frittés afin de réaliser la membrane en couche mince déposée sur support mécanique poreux. Ces études ont permis de comprendre les mécanismes gouvernant le procédé de dépôt par électroless et de l'appliquer à la réalisation de membranes qui ont ensuite été testées pour leur propriétés de perméation vis à vis de l'hydrogène.

Catalytic combustion provides us an efficient approach for the utilization and mitigation of methane, the major component of natural gas as well as an important greenhouse gas in global warming. From the research of catalytic combustion of methane, better understandings as well as solutions to the current methane-related problems can be obtained. This study investigates lean methane combustion on palladium-based catalysts. Catalysts activities were tested through ignition and extinction experiments. Several pretreatments and their influence were studied. Instrumental neutron activation analysis (INAA) and x-ray diffraction (XRD) were used as characterization tools for the catalysts. It was found that after being reduced, catalysts had stable and excellent abilities for methane conversion. However, these abilities were strongly compromised by additional water in the feeds. XRD results, combined with other testing results, implied that reduction produced the most active samples, while INAA revealed the real Pd concentrations of these catalysts. / Chemical Engineering

Dissertation (Ph.D.)--Worcester Polytechnic Institute. / Keywords: Hydrogen; synthesis; Pd-Cu; metallic membranes; PD. Includes bibliographical references (leaves 331-346 ).

The degradation of phosphate triesters is efficiently catalyzed by organophosphate hydrolases (OPH). While a number of recent studies have focused on optimizing the rate of hydrolysis observed with the native enzyme, no dinuclear complexes that mimic the function of OPH have been reported or investigated. Our present research focuses on the synthesis of dinuclear metal complexes and on the study of their catalytic abilities. An important aspect of this research concerns the investigation of the coordination chemistry of dinuclear ligands designed to hold two metal cations in well defined positions. The ability of the different complexes to catalyze the degradation of thiophosphate triester is presented. Out of several complexes studied, ortho-metallated Pd (II) complexes have been found to display the highest catalytic activity for the hydrolysis of parathion.

This thesis presents the development of new palladium-catalyzed transformations involving synthesis and application of allylborane reagents. In these reactions various palladium sources, including pincer complexes and commonly used catalysts were applied. A new transformation for allylation of aldehyde and imine substrates was devised using allyl acetates, diboronate reagents and catalytic amounts of Pd2(dba)3. By employment of commercially available chiral diboronates enantioenriched homoallyl alcohols could be obtained. We have also developed a palladium-catalyzed method for synthesis of functionalized allylboronic acids from vinyl cyclopropane, vinyl aziridine, allyl acetate and allyl alcohol substrates using diboronic acid as reagent. In this process a highly selective selenium based pincer-complex was used as catalyst. The resulting allylboronic acid products were converted to potassium trifluoro(allyl)borates or allylboronates. The functionalized allylboronic acids generated in the above procedure were employed as reagents in two synthetic transformations. One of these transformations involves a palladium(0)-catalyzed coupling reaction between allylboronic acids and aryl iodides. The reaction was regioselective for the branched allylic product, typically difficult to prepare in the absence of directing groups. We also developed another transformation for allylation of aldehydes with allyl alcohols via allylboronic acid intermediate. This procedure can be performed as a simple one-pot sequence affording homoallyl alcohols with excellent stereo- and regioselectivity.

Graduation date: 1991

The regioselectivity in Pd(0)-catalyzed direct arylation of pyrrole, thiophene, and indole can be improved by blocking some of the reactive sites with a chloride group, leading to increased yields of the desired regioisomers. Competition experiments and computational studies show that the blocking group also activates the substrates toward arylation. Due to the activated nature of chlorinated heteroaromatics, rare and sought after regioisomers, such as 3-arylthiophenes, can be obtained under mild conditions in good yields. Chlorine-bearing thiophenes arylated at C3 and C4 have the potential to undergo controlled regioregular polymerization under conditions developed in the field of polythiophene chemistry. Mechanistic studies support the hypothesis that the arylation of the substrates under investigation likely proceeds via the CMD transition state.

This research is focused on development of routes towards the rational design of nanoparticle catalysts. Primarily, it is focused on two main projects; (1) the use of imidazolium-based ionic liquids (ILs) as greener media for the design of quasi-homogeneous nanoparticle catalysts and (2) the rational design of heterogeneous-supported nanoparticle catalysts from structured nanoparticle precursors. Each project has different studies associated with the main objective of the design of nanoparticle catalysts.<p> In the first project, imidazolium-based ionic liquids have been used for the synthesis of nanoparticle catalysts. In particular, studies on recyclability, reuse, mode-of-stability, and long-term stability of these ionic-liquid supported nanoparticle catalysts have been done; all of which are important factors in determining the overall greenness of such synthetic routes. Three papers have been published/submitted for this project. In the first publication, highly stable polymer-stabilized Au, Pd and bimetallic Au-Pd nanoparticle catalysts have been synthesized in imidazolium-based 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6) ionic liquid (Journal of Molecular Catalysis A: Chemical, 2008, 286, 114). The resulting nanoparticles were found to be effective and selective quasi-homogeneous catalysts towards a wide-range of hydrogenation reactions and the catalyst solution was reused for further catalytic reactions with minimal loss in activity. The synthesis of very pure and clean ILs has allowed a platform to study the effects of impurities in the imidazolium ILs on nanoparticle stability. In a later study, a new mode of stabilization was postulated where the presence of low amounts of 1-methylimidazole has substantial effects on the resulting stability of Au and Pd-Au nanoparticles in these ILs (Chemical Communications, 2009, 812). In further continuation of this study, a comparative study involving four stabilization protocols for nanoparticle stabilization in BMIMPF6 IL is described, and have shown that nanoparticle stability and catalytic activity of nanoparticles is dependent on the overall stability of the nanoparticles towards aggregation (manuscript submitted).<p> The second major project is focused on synthesizing structurally well-defined supported catalysts by incorporating the nanoparticle precursors (both alloy and core shell) into oxide frameworks (TiO2 and Al2O3), and examining their structure-property relationships and catalytic activity. a full article has been published on this project (Journal of Physical Chemistry C, 2009, 113, 12719) in which a route to rationally design supported catalysts from structured nanoparticle precursors with precise control over size, composition, and internal structure of the nanoparticles has been shown. In a continuation of this methodology for the synthesis of heterogeneous catalysts, efforts were carried out to apply the same methodology in imidazolium-based ILs as a one-pot media for the synthesis of supported-nanoparticle heterogeneous catalysts via the trapping of pre-synthesized nanoparticles into porous inorganic oxide materials. Nanoparticle catalysts in highly porous titania supports were synthesized using this methodology (manuscript to be submitted).

The development of new, improved methods for forming carbon–carbon and carbon–heteroatom bonds is the basic goal in synthetic organic chemistry. In the Lautens group, many recent advances have been made using late transition metals such as rhodium and palladium. One such research project involves the synthesis of indoles through tandem C–N and C–C coupling reactions using gem-dibromoolefin starting materials, and this area serves as a starting point for the research described. Chapter 1 describes a method by which the tandem use of gem-dibromoolefins can be halted to give intramolecular monocoupling reactions, maintaining one of the carbon–bromine bonds which can serve as a useful handle for further functionalization. The use of copper as a catalyst is key to this reaction, as it features a unique mechanism for carbon–heteroatom bond formation. Benzofurans and benzothiophenes can be prepared by this method. Chapter 2 describes the synthesis of 2-bromoindoles using an intramolecular Buchwald–Hartwig amination of gem-dibromoolefins. It is found that the products are more reactive towards palladium(0) than the starting material, and the use of a bulky phosphine ligand which facilitates reversible oxidative addition is required. This represents one of the first catalytic applications of this step in synthesis. Chapter 3 further explores the concept of reversible oxidative addition in a novel carbohalogenation reaction of alkenes. Aryl iodides tethered to alkenes are treated with a palladium(0) catalysts, which can undergo the basic steps of oxidative addition, carbopalladation, and novel sp2 carbon–iodine reductive elimination. This process is remarkably simple in concept, and is a waste-free, atom economically method for preparing new carbon–carbon bonds. Chapter 4 discusses various limitations to the carbohalogenation methodology, and seeks to overcome these problems. The use of aryl bromide starting materials can be accomplished by adding an iodide source to the reaction, allowing halide exchange of palladium(II) intermediates to occur. Intermolecular and asymmetric variants are also explored. Computational studies are discussed which reveal useful mechanistic details of the catalytic cycle, and this information is used in the development of novel phosphine ligands.

Since recognizing the significance of reversible oxidative addition of palladium into aryl halides in the synthesis of 2-bromo-indoles, the Lautens group has focused on unusual carbon-halogen reductive eliminations. These efforts led to the discovery of the novel palladium-catalyzed inter- and intramolecular carbohalogenation reaction – the formal addition of an sp2 carbon–iodide bond across an alkene. One current research direction is utilizing a range of aryl halides and pseudohalides as starting materials for carbohalogenation chemistry. This thesis describes complementary research, focusing on the expansion of functional group scope. Carbohalogenation has been developed to synthesize novel products including heteroaromatic compounds and 7-membered rings. Polyunsaturated aryl iodide substrates were investigated with the goal of performing domino carbohalogenation. Ultimately, the successful halogen exchange process was combined with domino carbohalogenation in an efficient halogen-exchange domino reaction. Additionally, preliminary studies on enantioselective carbohalogenation, and functionalization of the neopentyl iodide products are also discussed.