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Thermocatalytic Plasma-Assisted Dry Reforming Of Methane Over Ni/Al2o3 Catalyst, Tyler Wong

Seton Hall University Dissertations and Theses (ETDs)

Plasma catalysis is an advantageous approach that combines the effects of plasma with the enhancements of a catalyst. By utilizing a nickel catalyst in the plasma discharge zone of a dielectric barrier discharge (DBD), it can give an enhancement to the electrical field, boost microdischarges, and increase conversion and selectivity rates of CH₄ and CO₂ in the dry reforming of methane (DRM) reaction.

Industrial application of nickel catalysts in DBD Plasma DRM process are limited by poor stability, which is caused by the sintering of active metal particles and coke deposition on the catalyst surface. In this work, …

Computationally-Driven Insights Into The Ligand Environments Of Materials For Catalysis And Separations, Stephen Vicchio

All Dissertations

Designing new catalytic and sorption materials is necessary to limit global temperature rise below 1.5 ◦C by 2050, while also meeting global energy demands. Climate change and energy production are not mutually exclusive; global population growth has direct impacts on global energy demands and climate. In both catalysis and adsorption applications, new technologies are needed to address these challenges. Catalysis can provide alternate, low-energy routes for converting low-value gases into higher-value chemical commodities, thus altering our current energy production. Likewise, new sorption materials can capture previously emitted CO₂ from decades of energy production from fossil fuels, thus helping to …

Syntheses, Photophysics, & Application Of Porphyrinic Metal-Organic Frameworks, Zachary L. Magnuson

USF Tampa Graduate Theses and Dissertations

Porphyrins are a group of heterocyclic macrocycles that play crucial roles in various biological processes such as electron transfer, catalysis, and sensing. Hemoglobin, which carries oxygen in the blood of mammals, and chlorophyll, which drives photosynthesis in plants and algae, are both porphyrins. The ability of porphyrins to bind metal ions and their unique electronic and photophysical properties make them an excellent platform for designing functional materials for various applications, often drawing inspiration from their function in nature. Metal-organic frameworks (MOFs) are a class of porous materials that have been extensively studied in recent years due to their high surface …

Improved Stoichiometric Synthesis Of Ccc-Nhc Pincer Rh Complexes And Catalytic Activity Towards Dehydrogenative Silylation And Hydrosilylation Of Alkenes, Enock Amoateng

Theses and Dissertations

N-Heterocyclic carbenes (NHCs) have attracted growing interest not only as successful ancillary ligands in a wide variety of transition-metal-catalyzed reactions but have also shown to offer photophysical and electrochemical properties. The metalation/transmetalation strategy using [Zr(NMe₂)₄] as initial metalating reagent offers an efficient approach to the preparation of CCC-NHC pincer complexes of the late transition metals such as Rh and Ir. In the process of investigating an intermediate and the mechanism of the metalation/transmetalation to Rh sequence, a mixed valent bimetallic CCC-NHC pincer Rh complex with two chloro ligands bridged between a [(CCC-NHC)Rh(III)] and a [Rh(I)(COD)] fragment …

Separation Of Organic Acids Through Direct Catalysis From Sugars, Katelyn Robinson

Chemical Engineering Undergraduate Honors Theses

Society relies on plastic products, whether they are single use or durable. A downside of plastic is that the most common type is a product of oil and oil is not only a limited resource but also a climate-damaging resource. Polylactic acid (PLA) is a bio-based, biodegradable plastic. However, the process of converting biomass to polylactic acid polymer has the largest environmental impact of the PLA production process, so alternative methods of conversion are needed (Moretti et al., 2021). The polylactic acid polymer can be made with lactic acid, which can be converted from glucose.

Novel Pathways To Tailor Charge And Spin In Materials And Investigating The Impact On Sensing And Electrochemical Energy Applications, Aruna Narayanan Nair

Open Access Theses & Dissertations

Catalysis is integral to our daily lives, as it streamlines and accelerates numerous chemical reactions essential for producing various materials, fuels, and chemicals. With the rising demand for clean, sustainable energy sources, optimizing catalytic materials and processes becomes increasingly vital. In the realm of renewable energy production, catalysis is crucial for efficiently converting energy from sustainable resources, such as solar, wind, and biomass, into chemical energy stored in fuels or directly into electrical energy.The electronic charge distribution in materials significantly influences their physical and chemical properties, facilitating the development of advanced electronic, optoelectronic, sensing, and energy conversion devices. Since catalysis …

The Kinetic Control Of Polymer Micelles; Chemical Functionality, Material Interactions, And Equilibration, Taylor Larison

Theses and Dissertations

Polymer micelles have found significant uses in areas such as, energy storage devices, catalysis, opto-electronics, drug-delivery, oil additives, and nanoreactors. In many of these applications the overall micelle size (aggregation number) and chemical functionalization determines performance. To progress towards more advanced materials synthesized from the facile bottom-up approach with polymeric micelles the implementation and study of thermodynamic handles were investigated. Here the kinetic control of micelles was studied across a range of applications; independent control over micelle functionality, the spatial orientation of multiple metal oxide nanoparticles in mesoporous materials via self-assembly, and the use of small-angle neutron scattering (SANS) to …

Copper-Catalyzed Dehydrogenative Decarboxylation Reactions Of Carboxylic Acids To Alkenes, Michael P. Stanton

Graduate Theses, Dissertations, and Problem Reports

Linear alpha olefins (LAOs) are important building blocks in the production of linear low-density polyethylene, a plastic used in products such as shrink wraps, plastic bags, tubing, plasticizers, among others. Commercial methods for generating LAOs utilize ethylene oligomerization, but this method is reliant on fossil fuels and leads to unselective product formation. Synthesis of LAOs from renewable resources, namely carboxylic acids, by decarbonylative dehydration strategies has been well studied, however, this method has inherent drawbacks rooted in the formation of internal olefin side-products through isomerization pathways. With the goal of avoiding internal isomerization, this thesis explores a dehydrogenative decarboxylation strategy …

Synthetic Methodologies Using Nucleophile-Electrophile Chemistry, Jacob C. Hood

Graduate Research Theses & Dissertations

Synthetic organic chemistry is a vital part of the modern world – making up 15-20% of the U.S. economy. New synthetic reactions can lower manufacturing costs and create more environmentally friendly processes. Substitution, addition, and superelectrophilic chemistry are potent tools to afford potentially essential compounds. The work outlined in this dissertation recounts the expansion of synthetic methodologies employing substrates with a wide range of electrophilicities toward synthesizing heterocyclic molecules. These concepts are summarized in chapter 1. Chapter 2: N-Heterocyclic alcohols are excellent substrates for superacid-promoted Friedel-Crafts reactions. The N-heterocyclic alcohol ionizes to produce reactive, dicationic intermediates, providing good to excellent …

Ambient Ammonia Synthesis Via Microwave-Catalytic Materials And Plasma Chemistry, Siobhan Brown

Graduate Theses, Dissertations, and Problem Reports

Ammonia is critical to supporting human life on earth because of its use as fertilizer. The Haber-Bosch process to produce ammonia has been practiced for over 100 years. This process operates at high pressure and temperature to overcome the thermodynamic and kinetic limitations of the ammonia synthesis reaction thus researchers have tried to overcome it for decades. At present this process represents 1% of global energy usage and 2.5% of global CO₂ emissions. The proposed chemical looping ammonia synthesis approach seeks to reduce the environmental impact of this critical process and to elucidate microwave-catalytic principles.

This research aims to …

First Principles Calculations To Investigate Surface And Catalytic Properties Of Materials For Green Energy Generation, Keerthan Raghavendra Rao

Theses and Dissertations--Chemistry

Climate change due to greenhouse gas build up in the earth’s atmosphere is an existential threat to humanity. To mitigate climate change, a significant shift from fossil fuels is necessary. Over the years, several renewable energy sources like solar, wind, geothermal etc. have been explored with the aim providing carbon-free energy. In this work, we focus on using density functional theory (DFT) methods to investigate key functional properties of materials of interest for applications in solar cells and catalytic conversion for energy generation. We show geometric effects of carboxylic acid binding on a transition metal surface to impact the deoxygenation …

Asymmetric Cuh-Catalyzed Reductive Coupling Of Allenamides With Carbonyl Electrophiles & Development Of Nanocatalysts For Heterogeneously Catalyzed Buchwald-Hartwig Amination, Raphael K. Klake

Theses and Dissertations

Many drugs and natural products contain multiple stereogenic carbons bearing heteroatoms throughout their carbon framework. Therefore, methods that can efficiently install multiple heteroatoms on a molecule are valuable. Reductive coupling reactions have been extensively studied, and the allylation of carbonyls via the reductive coupling approach has been a key method for generating chiral tertiary and secondary allylic alcohols. This work utilizes inexpensive Cu for the asymmetric reductive coupling of allenamides with carbonyls to simultaneously install two heteroatoms (oxygen and nitrogen) on the product. These molecules have a polarity profile that make them difficult to make using traditional methods. Herein, we …

Class A Sortases: Structures And Alternative Substrate Binding And Cleavage, Brandon Vogel

WWU Graduate School Collection

Sortases, consisting of classes A-F, are cysteine transpeptidases found in the cell wall of Gram-positive bacteria. They play a crucial role in ligating proteins to the cell wall that are responsible for cell adhesion, immune evasion, host cell invasion, and nutrient acquisition through a transpeptidation reaction. Consequently, they are an attractive therapeutic target. Class A sortases are also utilized in protein engineering applications such as sortase-mediated ligations and sortagging. Despite extensive research in the past two decades, gaps persist in understanding how class A sortases recognize their substrates, primarily due to a lack of structural information on sortases non-covalently bound …