Digital Commons Network^™

Development Of Ultra-Low Loading Of Compressive Pt Lattice Cathode Catalyst On Highly Stable Support For Pemfc Automotive Applications, Tianyuan Xie

Theses and Dissertations

The major barriers in the commercialization of the fuel cell technology for automotive applications are the cost and durability of the Pt catalyst and the support stability at high potentials. The U.S. Department of Energy (DOE) targets direct hydrogen fuel cell systems for transportation to meet 65% peak-efficiency, 5,000 hour durability with a mass production cost of $40/kW by 2020. Currently in 2015, the system can be operated at peak energy efficiency of 60% for 3,900 hours with cost of $55/kW. To meet these targets, precious metal loadings must be greatly reduced without altering the catalyst stability. The primary objective …

Surface Modification Of Nanodiamond And Its Incorporation In Nanodiamond/Peek Nanocomposites, Zahidul Wahab

Theses and Dissertations

The continued miniaturization of electronic device components requires new lightweight polymers with high thermal stability, high thermal conductivity, low electrical conductivity, and low dielectric constant. Composites of nanodiamond (ND) and poly(ether ether ketone) (PEEK) are candidates for these applications due their unique combination of properties. The objectives of this research are to explore new routes for surface functionalization of nanodiamond (ND), develop methods for maximizing dispersion of ND as a nano-scale filler in PEEK, and characterize the effect of dispersed ND on the mechanical, thermal and dielectric properties of ND/PEEK composites. Initial attempts to disperse different kinds of commercially available, …

Impact Of Formulation And Processing Parameters On Mechanical Properties Of Magadiite/Elastomer Composites, Yating Mao

Theses and Dissertations

This work seeks a better understanding of mechanical reinforcement and energy dissipation in elastomer composites containing the layered silicate magadiite (MGD, Na2Si14O29·nH2O). We characterized the elastomer’s accessibility into MGD interlayer spaces and studied the factors that influence the composite mechanical properties. We also compare the mechanical reinforcement of MGD with montmorillonite (MMT, a layered aluminosilicate clay mineral), which is widely used as filler in other kinds of nanocomposites. The study explores the grafting chemistry, vulcanization, and reinforcement mechanism in MGD/elastomer composites, which may help us to formulate the platelet/elastomer composites with superior mechanical properties and performance in the future. We …

Development Of Highly Active And Stable Hybrid Cathode Catalyst For Pemfcs, Won Suk Jung

Theses and Dissertations

Polymer electrolyte membrane fuel cells (PEMFCs) are attractive power sources of the future for a variety of applications including portable electronics, stationary power, and automobile application. However, sluggish cathode kinetics, high Pt cost, and durability issues inhibit the commercialization of PEMFCs. To overcome these drawbacks, research has been focused on alloying Pt with transition metals since alloy catalysts show significantly improved catalytic properties like high activity, selectivity, and durability. However, Pt-alloy catalysts synthesized using the conventional impregnation method exhibit uneven particle size and poor particle distribution resulting in poor performance and/or durability in PEMFCs. In this dissertation, a novel catalyst …

In Situ Ir Spectroscopic Investigation Of Noble Metal Catalysts Related To The Reduction Of Automotive Exhaust Emissions, Zhiyong Wang

Theses and Dissertations

The reduction of automotive exhaust emissions has been one of the hottest topics in catalysis community since 1970s. Thanks to the development of three-way catalysts, main auto-exhaust pollutants, such as carbon monoxide, nitrogen oxides and unburned hydrocarbons, can be removed simultaneously. Nowadays, diesel engines and lean-engines become more and more popular due to their high fuel-efficiency and low CO2 emissions. Unfortunately, conventional three-way catalysts are not effective at reducing the NOx emissions from these engines due to the excess oxygen in the exhaust stream. Platinum catalysts were found to be highly active for selective NO reduction with hydrocarbons in excess …

Preparation And Characterization Of Pt-Ru Bimetallic Catalysts Using Electroless Deposition Methods And Mechanistic Study Of Re And Cs Promoters For Ag-Based, High Selectivity Ethylene Oxide Catalysts, Weijian Diao

Theses and Dissertations

Pt-Ru bimetallic catalysts are widely used for direct methanol fuel cells, biomass upgrading and hydrocarbon refining and offer unique properties compared to Pt or Ru monometallic catalysts due to ensemble effects, electronic effects, and/or bifunctional effects. To achieve better performance, strong metal-metal interactions and true bimetallic surface are needed. Electroless deposition (ED) methods are used in our laboratory to synthesize such bimetallic catalysts. In this study, two series of Ru@Pt/C (Pt deposited on Ru surfaces) and Pt@Ru/C (Ru deposited on Pt surfaces) catalysts have been synthesized. Characterization data from temperature programmed reduction (TPR), selective chemisorption, X-ray photoelectron spectroscopy (XPS), and …

Supported Group Ib-Pd Bimetallic Catalysts Prepared By Electroless Deposition And Galvanic Displacement For Selective Hydrogenation Of Acetylene, Yunya Zhang

Theses and Dissertations

Ethylene is the building block for many chemical intermediates in the petrochemical industry. The current worldwide ethylene production is over 150 million tons per year and demand increases by 3-5% annually. However, ethylene produced from steam cracking of light naptha contains up to 2% acetylene which acts as a poison for the downstream ethylene polymerization catalysts. Selective hydrogenation of acetylene in the ethylene stream using supported Pd catalysts is the industrially preferred method of lowering acetylene to acceptable ppm levels (< 5 ppm). Due to inferior selectivity at high acetylene conversion and the formation of “green oil”, or ethylene/acetylene oligomers, during reaction, small amounts of Group IB metals have been added to improve the performance of current generation catalysts. However, the bimetallic effects of the above additives have not been experimentally confirmed, possibly because the conventional methods of catalyst preparation result in both monometallic and bimetallic particles with varying compositions. This in turn makes it difficult to determine the position of the two metallic components, and bimetallic interactions typically occur only when the two metals form proximal contact instead of separate particles. In this study, a series of Ag- and Au-Pd/SiO2 bimetallic catalysts were prepared by electroless deposition (ED) with incremental and controlled coverages of Ag and Au on Pd. The selectivity of acetylene to ethylene and turnover frequencies of acetylene conversion were enhanced at high coverages of Ag and Au on Pd surfaces due to the transition of acetylene adsorption modes, which was further confirmed by the kinetics of acetylene hydrogenation. The similar performance trends for Ag- and Au-Pd/SiO2 suggest that the bimetallic effect for these catalysts was likely geometric and not electronic in nature. For comparison, a series of reverse Pd-Ag/SiO2 bimetallic catalysts where variable coverages of Pd were deposited onto Ag surfaces was prepared using galvanic displacement (GD) of Ago by Pd2+ to further explore the nature of bimetallic effects for selective acetylene hydrogenation. Unlike for the earlier case for Ag on Pd surfaces using ED, for samples prepared by GD there was considerably diffusion of Pd into the Ag lattice to give greater electronic interactions between these two metals, which limited selectivity of acetylene hydrogenation to form ethylene.

Selective Synthesis And Characterization Of Single-Site Hy Zeolite-Supported Rhodium Complexes And Their Use As Catalysts For Ethylene Hydrogenation And Dimerization, Konstantin Khivantsev

Theses and Dissertations

Single-site Rh(CO)2, Rh(C2H4)2 and Rh(NO)2 complexes anchored on various dealuminated HY zeolites can be used as precursors for the selective surface mediated synthesis of well-defined site-isolated Rh(CO)(H)x complexes. DFT calculations and D2 isotope exchange experiments provide strong evidence for the formation of a family of site isolated mononuclear rhodium carbonyl hydride complexes (including the first examples of RhH complexes with undissociated H2 ligands): Rh(CO)(H2), Rh(CO)(H)2, and Rh(CO)(H). The fraction of each individual complex formed varies significantly with the Si/Al ratio of the zeolite and the nature of the precursor used.

HY zeolite-supported mononuclear Rh(CO)2 complexes are remarkably active in ethylene …

Engineered 3d Microenvironments To Direct Osteogenic Differentiation And Modulate Inflammation, Katherine Elizabeth Rutledge

Theses and Dissertations

Current methods of treating critical size bone defects (CSDs) include autografts and allografts, however both present major limitations including donor-site morbidity, risk of disease transmission, and immune-rejection. Tissue engineering provides a promising alternative to circumvent these shortcomings through the use of stem cells, three dimensional (3D) scaffolds, and growth factors. Cells receive signals from their microenvironment that determine cell phenotype, and a combination of physical cues and chemical factors is thought to have the most profound influence on stem cell behavior. A major focus of tissue engineering strategies is scaffold design to recapitulate in vivo microenvironmental architecture to direct stem …