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The Unique Electrochemical Reactivity Of Small Metal Nanoparticles., Rafael A. Masitas Dec 2015

The Unique Electrochemical Reactivity Of Small Metal Nanoparticles., Rafael A. Masitas

Electronic Theses and Dissertations

This dissertation describes the factors controlling metal nanoparticle (NP) oxidation, using Au oxidation in Br- and Ag oxidation in acid as model systems. We found that the oxidation potential depends on size, surface charge, and electrode material. Size has a dramatic effect, shifting about 200 mV from > 200 nm diameter down to 4 nm diameter. The shift is more dramatic below 4 nm. 2.3 nm average diameter Au NPs oxidized in the 300-500 mV range and 1.5 nm average diameter Au NPs displayed several sharp peaks from 200 mV to as low as -200 mV. These smallest Au NPs show …


Electrochemical Formation Of One-Dimensional Metal Nanostructures Across Microgaps Electrodes For Resistive Switching And Optical Sensing Applications., Nidhi Shah Dec 2015

Electrochemical Formation Of One-Dimensional Metal Nanostructures Across Microgaps Electrodes For Resistive Switching And Optical Sensing Applications., Nidhi Shah

Electronic Theses and Dissertations

This dissertation focuses on the electrochemical formation of one-dimensional (1D) Ag nanostructures (in particular nanowires and nanochains) directly on electrode surfaces or gap of two electrodes. Ag nanowires (NWs) and nanorods (NRs) grow directly on glass/indium tin oxide (ITO) surfaces from electrode-attached Au nanoparticle seeds in the presence of cetyltrimethylammonium bromide (CTAB) at appropriate potentials with a 5-15 % yield and the average length ranging from 100 nm to 3 µm for growth times of 30 to 120 min. This method failed when trying to grow Ag NRs/NWs across 5 µm Au electrode gaps. Interestingly, applying voltage in air leads …


Application Of Surface Chemistry At The Interface Of Mesoporous Tio2 Films For Stable And High Efficiency Dye-Sensitized Solar Cells., Tulashi Luitel Aug 2015

Application Of Surface Chemistry At The Interface Of Mesoporous Tio2 Films For Stable And High Efficiency Dye-Sensitized Solar Cells., Tulashi Luitel

Electronic Theses and Dissertations

Solar energy is widely believed to be the most promising renewable energy source to fulfill the ever-increasing energy demand from human society now and into the future. Dye-sensitized solar cells (DSSCs) have been explored as a potentially low-cost alternative to silicon solar cell technology due to their lower fabrication costs compared to crystalline semiconductor photovoltaics. However, the optimized efficiency for DSSCs has not been achieved yet, and the chemical stability between dye and semiconductor has also not been addressed completely. In this research, we applied the following four main strategies to prepare photoanodes used in DSSCs with the aim of …


Phosphinimine Zinc Complexes And Neutral Phosphinimines For Ring Opening Polymerization Of Lactides., Rajesh Thapa Aug 2015

Phosphinimine Zinc Complexes And Neutral Phosphinimines For Ring Opening Polymerization Of Lactides., Rajesh Thapa

Electronic Theses and Dissertations

Achiral arenesulfonates ligands having a (NNN) or (NNO) side arm have been developed (Chapter 2) and their respective zinc ethyl complexes, NNNZnEt 3.2 and NNOZnEt 3.3, have been synthesized and characterized using spectroscopic methods (Chapter 3). NNNZnEt as well as NNOZnEt complexes are stable under nitrogen atmosphere. In the NNOZnEt 3.3 complex the protons associated with the pendant (dimethylamino)ethyl arm are broad indicating that a fluxional process is operative, most likely dissociation of the (dimethylamino)ethyl arm at 25 °C in CD2Cl2. The fluxional behavior present in the 1H NMR spectrum of 3.2 could be arrested by cooling the CD2Cl2 solution …


Optical And Sensing Properties Of Various Shaped Gold Nanoplates And Highly Controlled Asymmetric Gold Nanoplate/Nanosphere Coupled Assemblies., Aiqin Fang Aug 2015

Optical And Sensing Properties Of Various Shaped Gold Nanoplates And Highly Controlled Asymmetric Gold Nanoplate/Nanosphere Coupled Assemblies., Aiqin Fang

Electronic Theses and Dissertations

With the development of a strategy to correlate the dark-field light scattering spectra of individual nanostructures with scanning electron microscopy (SEM) and atomic force microscopy (AFM) images of the same nanostructures, we were able to investigate several interesting optical properties of Au nanoplates (NPs) and asymmetrically-coupled Au nanospheres (NSs) attached to Au NPs with a high level of control. The light scattering spectra of the NP/NS coupled structures depend strongly on the location of NS attachment on the NP. Attachment of multiple NSs at the edge/vertex sites leads to a unique synergistic effect. In contrast to the uniform distribution of …


Analysis Of Anacardic Acid On The Surface Of Pelargonium × Hortorum Using Matrix Assisted Laser Desorptoin Ionization Mass Spectrometry Imaging., Bryan Edward Wessel 1989- May 2015

Analysis Of Anacardic Acid On The Surface Of Pelargonium × Hortorum Using Matrix Assisted Laser Desorptoin Ionization Mass Spectrometry Imaging., Bryan Edward Wessel 1989-

Electronic Theses and Dissertations

The biosynthetic pathway leading to the production of anacardic acids (AnAcs) in glandular trichomes on the surface of geranium plants remains unclear. Anacardic acids are salicylic acid derivatives known to possess various medicinal benefits. Gene silencing techniques, such as RNA interference, could be useful in determining specific enzymes involved in the synthesis of AnAcs. However, it is first necessary to develop methodologies to image AnAcs. In this project, both fluorescence (FL) and mass spectral imaging (MSI) were tested. Our results indicate that cellular imaging of AnAcs, via FL, is not suitable because the spectral ranges of absorption and emission of …


Sulfur-Oxidation Enhances Nitrile Hydration In Bioinspired Ruthenium Complexes : Catalytic, Kinetic, And Dft Investigations., Davinder Kumar May 2015

Sulfur-Oxidation Enhances Nitrile Hydration In Bioinspired Ruthenium Complexes : Catalytic, Kinetic, And Dft Investigations., Davinder Kumar

Electronic Theses and Dissertations

The current dissertation focuses on the effects of sulfur‒oxidation on nitrile hydration activity of a series of ruthenium(II) complexes inspired by nitrile hydratase (NHase). NHase catalytically hydrates nitriles to amides at a low spin non‒heme Fe(III) or non‒corrin Co(III) metal center. The active‒site employs a N2S3X type donor set using two carboxamido nitrogens and three cofacial cysteinic sulfurs that are present in distinct oxidation states as sulfinate (RSO2¯), sulfenate (RSO¯), and thiolate (RS¯). The apical site is occupied by substrate or solvent. A lack of sulfur‒oxidation renders the enzyme inactive. Three precatalysts, LnRuPPh3 (n = 1‒3), are employed to assess …


A Study Of The Catalytic And Chemical Properties Of Palladium And Palladium-Silver Monolayer Protected Clusters., Luther Benjamin Hutcherson May 2015

A Study Of The Catalytic And Chemical Properties Of Palladium And Palladium-Silver Monolayer Protected Clusters., Luther Benjamin Hutcherson

Electronic Theses and Dissertations

This thesis describes a study of the ligand chemistry of Pd Monolayer-Protected Clusters (MPCs) synthesized in the presence of octylamine. MPCs consists of a metal core surrounded by various organic stabilizers. Pd MPCs coated with alkanethiols, alkylamine, dendrimers, surfactants, and polymers have recently been explored for catalysis applications.Pd MPCs coated with alkylamines are more catalytically active than alkanethiols for hydrogentation/isomerization of allyl alcohol, but at shorter chain lengths are unstable in H2. We explored Pd MPCs synthesized in the presence of octylamines and discovered that the ligands attach to Pd as octanenitrile. This amine to nitrile conversion is catalyzed by …