Physical Sciences and Mathematics Commons^™

H2 Oxidation Over Supported Au Nanoparticle Catalysts: Evidence For Heterolytic H2 Activation At The Metal-Support Interface, Todd N. Whittaker, K. B. Sravan Kumar, Christine Peterson, Meagan N. Pollock, L. C. Grabow, Bert D. Chandler

Chemistry Faculty Research

Water adsorbed at the metal-support interface (MSI) plays an important role in multiple reactions. Due to its importance in CO preferential oxidation (PrOx), we examined H₂ oxidation kinetics in the presence of water over Au/TiO₂ and Au/Al₂O₃ catalysts, reaching the following mechanistic conclusions: (i) O₂ activation follows a similar mechanism to that proposed in CO oxidation catalysis; (ii) weakly adsorbed H₂O is a strong reaction inhibitor; (iii) fast H₂ activation occurs at the MSI, and (iv) H₂ activation kinetics are inconsistent with traditional dissociative H₂ chemisorption on metals. Density …

Trace Element Geochemistry And Nd-Sr Isotope Systematics Of Scheelite From The Thunder Creek And 144 Gap Deposits, Timmins, Ontario: Implications For Timing And Genesis Of Gold, Annika Van Kessel

Electronic Thesis and Dissertation Repository

The age of the youngest gold event at the Timmins West Mine is unknown. Scheelite geochemistry and geochronology at the TWM were constrained using WDS and EDS mapping, LA-ICPMS and MC-ICPMS analytical techniques. Trace element analyses by LA-ICPMS revealed scheelites mineralized from a common and oxidized fluid. Samarium-Neodymium isotopic analyses of 15 scheelite grains yielded a linear regression isochron with a corresponding age of 2587 +/- 49 Ma (MSWD = 2.5) and εNdi, calculated from CHUR, of 1.01 ± 0.11 (2SD). A second internal isochron from a single scheelite grain yielded an age of 2516 +/- 88 Ma (MSWD = …

Gold-Catalyzed Conversion Of Lignin To Low Molecular Weight Aromatics, Yang Song, Justin K. Mobley, Ali Hussain Motagamwala, Mark Isaacs, James E. Dumesic, John Ralph, Adam F. Lee, Karen Wilson, Mark Crocker

Chemistry Faculty Publications

A heterogeneous catalyst system, employing Au nanoparticles (NPs) and Li–Al (1 : 2) layered double hydroxide (LDH) as support, showed excellent activity in aerobic oxidation of the benzylic alcohol group in β-O-4 linked lignin model dimers to the corresponding carbonyl products using molecular oxygen under atmospheric pressure. The synergistic effect between Au NPs and the basic Li–Al LDH support induces further reaction of the oxidized model compounds, facilitating facile cleavage of the β-O-4 linkage. Extension to oxidation of γ-valerolactone (GVL) extracted lignin and kraft lignin using Au/Li–Al LDH under similar conditions produced a range of aromatic monomers in high yield. …

Cerberus-Type Trisanionic Trisnhc And Its Zwitterionic Gold And Silver Complexes, Maleek Montgomery, Daniela Tapu

Master of Science in Chemical Sciences Theses

While early efforts have been made to explore the chemistry of neutral multitopic nonchelating N-heterocyclic carbenes (NHCs), limited progress has been made in the development of their anionic counterparts. This thesis describes the synthesis and characterization of a novel trianionic NHC. The corresponding thione was generated through an NMR experiment of the free carbenes with an excess of sulfur. The utility of this novel triscarbene as a ligand in organometallic chemistry has been proven by the construction of homotrimetallic systems. The resulting zwitterionic metal complexes of type [(MPPh)₃(NHC)] (M = Au or Ag) have been fully characterized by …

Coinage Metal Chalcogenide Clusters With N-Heterocyclic Carbene Ancillary Ligands, Alex Polgar

Electronic Thesis and Dissertation Repository

This thesis describes the synthesis and characterization of homo- and heterometallic group 11 – group 16 clusters with N-heterocyclic carbene (NHC) ligands. The clusters were prepared from reactive group 11 trimethylsilylchalcogenolate reagents (NHC-M-ESiMe3; M = Cu, Au; E = S, Se, Te) by silane deprotection reactions with phosphine- or phosphite-solubilized group 11 acetates (R3P-M-OAc; M = Cu, Ag, Au). Clusters were characterized by combustion analysis and spectroscopic methods in solution and the solid state. The clusters were phosphorescent at low temperatures with emission energies that depend on the metal/chalcogen composition, ancillary NHC ligand, cluster geometry and nuclearity, and local environment. …

Study On The Surface Features Of Preg-Robbing Carbonaceous Matter During Oxidation Treatment, Mana Pourdasht

Electronic Thesis and Dissertation Repository

Carbonaceous gold ores have the ability to adsorb gold (I) cyanide from leach solutions during processing. This phenomenon, known as preg-robbing, is responsible for poor recoveries as the carbonaceous materials of the ore compete with activated carbon used during the leaching and adsorption phase of processing. Chemical oxidation of carbonaceous materials by different reagents has been utilized to investigate and compare the mechanism of Au (CN)₂ adsorption onto carbonaceous materials prior to and following the treatment.

The procedure for characterization of the carbonaceous materials (plain and modified) in the sample combines the use of several analytical techniques and test …

Evaluating Differences In The Active-Site Electronics Of Supported Au Nanoparticle Catalysts Using Hammett And Dft Studies, G. Kumar, Luke Tibbitts, Jaclyn Newell, Basu Panthi, Ahana Mukhopadhyay, Robert M. Rioux, Christopher J. Pursell, M. Janik, Bert D. Chandler

Chemistry Faculty Research

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 …

Lithography-Free, Omnidirectional, Cmos-Compatible Alcu Alloys For Thin-Film Superabsorbers, Mariama Rebello De Sousa Dias, Chen Gong, Zachary A. Benson, Marina S. Leite

Physics Faculty Publications

Superabsorbers based on metasurfaces have recently enabled the control of light at the nanoscale in unprecedented ways. Nevertheless, the sub‐wavelength features needed to modify the absorption band usually require complex fabrication methods, such as electron‐beam lithography. To overcome the scalability limitations associated with the fabrication of metallic nanostructures, engineering the optical response of superabsorbers by metal alloying is proposed, instead of tuning the geometry/size of the nanoscale building blocks. The superior performance of thin film AlCu alloys as the metallic component of planar bilayer superabsorbers is numerically demonstrated. This alloy outperforms its pure constituents as well as other metals, such …

Engineering Surface Amine Modifiers Of Ultrasmall Gold Nanoparticles Supported On Reduced Graphene Oxide For Improved Electrochemical Co2 Reduction, Yong Zhao, Caiyun Wang, Yuqing Liu, Douglas R. Macfarlane, Gordon G. Wallace

Australian Institute for Innovative Materials - Papers

Ultrasmall gold (Au) nanoparticles with high mass activity have great potential for practical applications in CO2electroreduction. However, these nanoparticles often suffer from poor product selectivity since their abundant low-coordinated sites are favorable for H2evolution. In this work, a catalyst, reduced graphene oxide supported ultrasmall Au nanoparticles (≈2.4 nm) is developed which delivers high Au-specific mass activities (>100 A g-1) and good Faradaic efficiencies (32-60%) for the CO2-to-CO conversion at moderate overpotentials (450-600 mV). The efficiencies can be improved to 59-75% while retaining the ultrahigh mass activities via a simple amine-modification strategy. In addition, an amine-structure-dependent effect is revealed: linear …

Electrodeposited Semiconductor Nanostructures & Epitaxial Thin Films For Flexible Electronics, Naveen Kumar Mahenderkar

Doctoral Dissertations

"Single-crystal Si is the bedrock of semiconductor devices due to the high crystalline perfection which minimizes electron-hole recombination, and the dense native silicon oxide which minimizes surface states. To expand the palette of electronic materials beyond planar Si, an inexpensive source of highly ordered material is needed that can serve as an inert substrate for the epitaxial growth of grain boundary-free semiconductors, photonic materials, and superconductors. There is also a need for a simple, inexpensive, and scalable fabrication technique for the growth of semiconductor nanostructures and thin films. This dissertation focuses on the fabrication of semiconducting nanowires (polycrystalline Ge & …