Physical Sciences and Mathematics Commons^™

Electrochemical Determination Of Surface Area-To-Volume Ratio For Metal Nanoparticle Analysis., Jay Narayan Sharma

Electronic Theses and Dissertations

This dissertation describes an electrochemical approach for measuring the surface area-to-volume ratio (SA/V) of electrode-attached metal nanoparticles (NPs), which was used to analyze their size, aggregation state, and porosity. This dissertation further describes the effect of the metal NP electrode assembly method on the SA/V, which is related to metal NP catalytic activity and stability. Cyclic voltammetry (CV) in acid electrolyte followed by anodic stripping voltammetry (ASV) in KBr electrolyte allows the electrochemical measurement of the SA/V of electrode-attached Au nanospheres (NSs). In CV, the forward scan produces a thin surface Au₂O₃ layer on the Au NSs. …

Homogeneous Ligand-Centered Hydrogen Evolution And Hydrogen Oxidation : Exploiting Redox Non-Innocence To Drive Catalysis., Andrew Z. Haddad

Electronic Theses and Dissertations

Hydrogen is a promising carbon-free fuel / energy carrier and is an essential building block for many industrial and agricultural processes. Rising energy demands have ignited interest in the development of carbon-free and carbon neutral energy sources. In this context, hydrogen is an attractive candidate—being energy-dense, carbon-free—and easily accessible through a two-electron reduction of water. Accordingly, many electrochemical homogeneous catalyst systems have been studied, with a focus on understanding the mechanism of hydrogen evolution proceeding through metal-hydride intermediates. However, there has been a renaissance in hydrogen evolution reaction (HER) catalyst design, with many groups implicating ligand redox non-innocence as a …

The Decline And Recovery Of Thermal Oxidative Stability Of Ultra-Low Sulfur Diesel Blends, Abigail Schoor Cohen

Electronic Theses and Dissertations

Dissertation supervised by Professor Bruce D. Beaver

The oxidative stability of ultra-low sulfur diesel (ULSD) has generally been expected to continuously decline over time. However, recent studies have suggested that it may fluctuate.^1-2 In this study, the oxidative stability of stored commercially purchased ULSD was monitored with a methanol extraction method.³ In this methodology, proposed by Hardy and Wechter, fuel blends are extracted with methanol before and after thermal stressing.⁴ The methanol-soluble layer contains the oxygenated and oxidizable components of the fuel (SMORS) and the change in this mass upon stressing thus represents the oxidative stability of …

Development Of Palladium Catalyzed Alkene Difunctionalization On Vinyl-Quinoline Type Substrate And Isolation Of Pd-Alkyl Intermediate, Lusha Xu

Electronic Theses and Dissertations

The synthesis of quinoline derivatives is a continuing issue facing organic chemists in both academia and industry. To address this problem, palladium-catalyzed alkene difunctionalization was developed to be a powerful and straightforward strategy of synthetic transformations for adding diversity to organic molecules. In this thesis, Pd-catalyzed olefin difunctionalization reactions of vinyl-quinoline type substrate via generating Pd-alkyl intermediates were mainly described. The reactions described herein are pursuing three significant goals: 1) to isolate and recrystallize Pd-alkyl complexes; 2) to achieve oxidation reactions on Pd-alkyl intermediate; and 3) to investigate stereochemistry of nucleopalladation step on vinyl-quinoline starting materials.

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 …

Kinetics And Mechanism Of Oxygen Delignification, Yun Ji

Electronic Theses and Dissertations

Considerable research has been conducted into the kinetics and selectivity of the oxygen delignification process to overcome limitation in its use. However most studies were performed in a batch reactor whereby the hydroxide and dissolved oxygen concentrations are changing during the reaction time in an effort to simulate tower performance in pulp mills. This makes it difficult to determine the reaction order of the different reactants in the rate expressions. Also the lignin content and cellulose degradation of the pulp are only established at the end of the experiment when the sample is removed from the batch reactor. To overcome …

Separation And Identification Of The 2,4-Dinitrophenylhydrazones Of The Oxidation Products Of Glycerol., Gwendolyn Parker Mcclure

Electronic Theses and Dissertations

No abstract provided.