Browsing by Subject "chemistry, physical"
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Item Bis(Imino)Acenaphthene (BIAN)-Supported Palladium(II) Carbene Complexes as Effective C-C Coupling Catalysts and Solvent Effects in Organic and Aqueous Media(2014) Crawford, Katherine A.; Cowley, Alan H.; Humphrey, Simon M.; Crawford, Katherine A.; Cowley, Alan H.; Humphrey, Simon M.The synthesis and catalytic properties of two new 1,2-acenaphthenyl N-heterocyclic carbene-supported palladium(II) catalysts are presented. The acenaphthenyl carbene has been prepared with mesityl or 1,5-diisopropyl N-aryl substituents. Comprehensive catalytic studies for the Suzuki coupling of aryl halides with aryl boronic acids have been conducted. In general, the diisopropyl-functionalised catalyst showed superior selectivity and reactivity. A comparison of the catalytic performances in dichloromethane, toluene and water at low temperatures (30- 40 degrees C) is also presented. Both catalysts were proficient in the homogeneous Suzuki coupling of aryl iodides, bromides and chlorides with boronic acids in dichloromethane. Similar reactions in water led to the formation of insoluble colloidal catalytic species that still exhibited high activity in the Suzuki reaction with aryl chlorides. Reactions performed in toluene showed intermediate results; partial catalyst decomposition led to concomitant homogeneous and heterogeneous catalysis. The heterogeneous palladium precipitates could be easily recovered by filtration and reactivated for subsequent use. Activation energies determined for aryl bromide-based Suzuki reactions were found to be in the range of 159-171 kJ mol(-1) in organic solvents and 111-116 kJ mol(-1) in water. The corresponding activation energy for the aryl chloride was found to be 322 kJ mol(-1) in water.Item Graphite Oxide Activated Zeolite NaY: Applications in Alcohol Dehydration(2013) Todd, Alexander D.; Bielawski, Christopher W.; Bielawski, Christopher W.A mixture of graphite oxide (GO) and the zeolite NaY (Si/Al = 5.1) was used to dehydrate various alcohols to their respective olefinic products. Using conditions optimized for 4-heptanol (15 wt% GO-NaY (1:1 wt/wt), 150 degrees C, 30 min), a series of secondary and tertiary aliphatic alcohols were cleanly dehydrated in moderate to excellent conversions (27.5-97.2%). Several primary alcohols were also dehydrated, although higher catalyst loadings (200 wt% GO-NaY (1 : 1) and longer reaction times (3 h) were required. The enhanced dehydration activity was attributed to the ability of GO to convert NaY to an acidic form and without the need for ammonium cation exchange and/or high temperature calcination.Item HRTEM and Molecular Modeling of the MoS 2-Co9 S 8 Interface: Understanding the Promotion Effect in Bulk HDS Catalysts(2012) Ramos, Manuel; Berhault, Gilles; Ferrer, Domingo A.; Torres, Brenda; Chianelli, Russell R.; Ferrer, Domingo A.As environmental regulations increase, more selective transition metal sulfide (TMS) catalytic materials for hydrotreating applications are needed. Highly active TMS catalysts become more and more desirable triggering new interest for unsupported Co-promoted MoS2-based systems that have high volumetric activity as reported here. Contrary to the common observation for alumina-supported MoS2-based catalysts, we found in our previous studies with dibenzothiophene (DBT) hydrodesulfurization (HDS) that the catalytic activity is directly proportional to the increase of surface area of the sulfide phases (Co9S8 and MoS2) present in Co-promoted MoS2 unsupported catalysts. This suggests that activity is directly connected with an increase of the contact surface area between the two sulfide phases. Understanding of the nature of the possible interaction between MoS2 and Co9S8 in unsupported catalytic systems is therefore critical in order to get a more generalized overview of the causes for synergy. This has been achieved herein through the detailed characterization by XRD, XPS, and HRTEM of the highly active Co9S8/MoS2 catalyst resulting in a proposed model for a Co9S8/MoS2 interface. This model was then subjected to a DFT analysis to determine a reasonable description of the surface contact region between the two bulk phases. Modelling of the interface shows the creation of open latent vacancy sites on Mo atoms interacting with Co and formation of direct Co-Mo bonds. Strong electron donation from Co to Mo also occurs through the intermediate sulfur atom bonded to both metals while an enhanced metallic character is also found. These changes in coordination and electronic properties are expected to favor a synergetic effect between Co and Mo at the proposed localized interface region between the two bulk MoS2 and Co9S8 phases.Item MnNiCoO4/N-MWCNT Nanocomposite Catalyst with High Selectivity in Membraneless Direct Formate Fuel Cells and Bifunctional Activity for Oxygen Electrochemistry(2015-02) Yu, Xingwen; Manthiram, Arumugam; Yu, Xingwen; Manthiram, Arumugam