Physical Sciences and Mathematics Commons^™

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, …

Friedel-Crafts Alkylation Of Benzene With A Superacid Catalyst, Josh T. Cutright

Undergraduate Honors Theses

Long-chain alkylbenzenes are industrially synthesized precursors to commercial surfactants such as laundry detergent. The currently used catalysts in the processes of their synthesis are corrosive and harmful to the environment. These problems can be avoided utilizing heterogeneous highly acidic catalysts. Solid catalysts do not corrode equipment and are relatively simple to remove from the post-reaction mixture. Phosphotungstic acid (PTA) supported on silica gel could be a possible catalyst due to its high acidity with an estimated pKa ≈ -13. The catalyst PTA-SiO₂ was prepared via the sol-gel method to covalently embed it in a silica support. The catalyst was …

Alkylation Of Benzene On Immobilized Phosphotungstic Acid, Kofi Kankam

Electronic Theses and Dissertations

Linear alkylbenzenes (LAB) are key intermediates in the synthesis of linear alkylbenzene sulfonate surfactants that are used in the manufacture of detergents. Production of LAB with traditional Lewis acids as catalysts, such as hydrofluoric acid, results in the formation of large amounts of toxic wastes and corrosion of industrial equipment. Phosphotungstic acid (PTA) has gained much attention in recent years as a solid catalyst for various alkylation reactions. This research work aims to develop a novel material based on PTA-containing silica gel, which can effectively catalyze LAB synthesis. Sol-gel synthesis of silica gel in the presence of PTA and tetraethyl …

Immobilization Of Phosphotungstic Acid On Silica Surface For Catalytic Alkylation Of Aromatic Compounds, Anastasia Kuvayskaya

Electronic Theses and Dissertations

Superacidic mesoporous materials containing covalently embedded PTA were synthesized by sol-gel method. Tetraethyl orthosilicate (TEOS) and phosphotungstic acid (PTA) were used as precursors in the synthesis, ionic and nonionic surfactants were used as pore-forming agents, the reaction proceeded in acidic media. TEM images revealed mesoporous structure with embedded PTA clusters. FT-IR spectra of obtained materials contained characteristic bands of PTA at 957 cm-1. Synthesized catalysts had high BET surface area and high concentration of acidic sites. Alkylation of 1,3,5-trimethylbenzene by 1-decene demonstrated high catalytic activity. The catalyst obtained with Pluronic P123 as a template was the most effective and resulted …

Visible Light Generation Of High-Valent Corrole-Manganese(V)-Oxo Intermediates And Biomimetic Studies Of The Oxidation Of Organic Sulfides Catalyzed By Manganese Corroles With Iodobenzene Diacetate, Davis Ray Ranburger

Masters Theses & Specialist Projects

High-valent transition metal-oxo intermediates play essential roles as active oxidizing species in enzymatic and biomimetic catalytic systems. Extensive research has been conducted on a variety of transition metal catalysts being studied as models for the ubiquitous cytochrome P450 enzymes. In doing so, the production of enzyme-like oxidation catalysts and probing studies on the sophisticated oxygen atom transfer mechanism are taking place.

In this work, visible-light irradiation of highly-photo-labile corrole-manganese(IV) bromates and chlorates was studied in two corrole systems with differing electronic environments, i.e. 5,10,15-trisphenylcorrole (H3TPC) and 5,10,15- tris(pentafluorophenyl)corrole (H3TPFC). In both systems, homolytic cleavage of the O- …

Thermally Robust And Redox Active Catalysts: Studying Their Behavior For Ethylene And L-Lactide Polymerization, Lauren Ashley Brown

Doctoral Dissertations

The development of homogenous single-site catalysts has significantly impacted the field of organometallic chemistry. The well-defined structures of homogenous catalysts make it less cumbersome to understand and develop methods to tailor these compounds for specific catalytic processes. Currently, polymerization catalysis is a major division in organometallic chemistry due to the global demand for polymeric materials such as polyethylene (PE) and polypropylene (PP), based on their low-cost feedstock, remarkable mechanical properties, and their use in a wide range of applications. However, bioplastics have become a highly sought-after alternative to conventional petrochemical-based plastics due to their biodegradability and derivatization from renewable resources. …

Development Of High Performance Gas Separation Membranes Through Intelligent Catalyst And Monomer Design, Kevin Richard Gmernicki

Doctoral Dissertations

Polymer membranes are a valuable tool for separating components of liquid and gas mixtures. Heavily inspired by biological systems, the idea of using the intrinsic properties of polymers to perform otherwise energy-intensive tasks is attractive for applications such as water desalination, natural gas sweetening, and post-combustion carbon capture. Of particular interest to our research group, post-combustion carbon capture is a promising potential solution aimed at reducing the carbon footprint involved with production, transportation, and storage of electrical energy generation.

Every year, the United States produces close to seven billion metric tons of carbon dioxide, of which a significant portion is …

Part 1: Design, Synthesis, And Evaluation Of Novel Gram-Positive Antibiotics Part 2: Synthesis Of Dihydrobenzofurans Via A New Transition Metal Catalyzed Reaction Part 3: Design, Synthesis, And Evaluation Of Bz/Gabaa Α6 Positive Allosteric Modulators, Christopher Michael Witzigmann

Theses and Dissertations

Part 1. Lead compound SK-03-92 represents a new scaffold for antibiotic drug discovery. Development of a new process for the synthesis of analogs has led to the development of a number of new ligands with even more potent activity against gram-positive bacteria, including drug-resistant strains of S. aureus. Compounds 36 and 38 represent some of the most potent analogs developed thus far, and preliminary results indicate that they are also not cytotoxic. Research into a Heck-mediated transition metal catalyzed pathway towards electron-rich stilbenoid analogs has greatly expanded the scope of future SAR studies. This development has led to 14 new …

Cobalt Mediated Oxidative Cyclizations: The Diastereoselective Synthesis Of Trans-Tetrahydrofuran Rings, Cory D.N. Palmer

Electronic Thesis and Dissertation Repository

The Mukaiyama oxidative cyclization has been a major area of study within the Pagenkopf group and within the field of THF containing natural products. This document contains a brief discussion of the major divisions of THF synthesis; S_N2, cycloadditions, and transition mediated strategies. The development of the Mukaiyama cyclization is described from the earliest applications of cobalt acac type ligand in Mukaiyama’s work to the initial discovery of the cyclization reactivity. Initial finding from the Mukaiyama group is shown, accompanied by its applications to the synthesis of mucosin, aplysiallene, and bullatacin. Previous attempts at improved catalyst design are …

Synthesis Of Diazonium Perfluoroalkyl(Aryl) Sufonimide (Pfsi) Zwitterions For Solid Acid Alkylation Catalysts, Husan Ahmad

Undergraduate Honors Theses

The final objective of this project is to create an environmentally friendly solid alkylation catalyst to replace the commercially available liquid acid catalysts, such as hydrofluoric acid and sulfuric acid, which are used in the petroleum industry. My research target is to synthesize the diazonium PFSI zwitterions, which can be chemically grafted on the silica as the solid alkylation catalyst. A 4-steps synthesis is designed to prepare the diazonium PFSI zwitterions. The first two steps were successfully completed in the lab. The first one is to prepare the starting material of 4-nitrobenzenesulfonamide from an ammonolysis reaction between 4-nitrobenzene sulfonyl chloride …

Developing Catalysts For Improving Direct Amide Formation, Courtney Carley

Summer Research

The widespread occurrence of the amide functional group in the pharmaceutical industry and its prevalence in biological structures such as proteins illustrate the huge impact that amides have on our daily lives. Current methods of forming amides are expensive and harmful to the environment, so there is a need for the development of greener processes for the formation of amides. The first objective of this research is to synthesize catalysts for the direct formation of amides from carboxylic acids and amines. Previously developed catalysts for this transformation are not active enough, and are thus rarely used. The new catalysts to …

Br[O/]Nsted Acid Catalyzed Asymmetric Allylation And Propargylation Of Aldehydes, Pankaj Jain

USF Tampa Graduate Theses and Dissertations

Carbonyl allylation and propargylation reactions have been an important tool for the stereocontrolled formation of carbon-carbon bonds for synthetic chemists. The chiral homoallylic and homopropargylic alcohols obtained from these reactions serve as versatile intermediates for the synthesis of natural and pharmaceutical products. Over the past three decades and continuing on, various synthetic groups around the globe have directed their research towards the efficient synthesis of these chiral moieties. In spite extensive research, asymmetric allylation and propargylation reactions remain an enduring challenge in organic chemistry.

Chapter 1 of this thesis describes the first phosphoric acid catalyzed asymmetric allylboration of aldehydes. We …

Synthesis Of Platinum And Platinum-Copper Branched Nanoparticles For Electrooxidation Of Methanol, Eric Courtland Taylor

Graduate Theses and Dissertations

Platinum and Pt alloys are among the most important heterogeneous catalysts for many organic reactions and electrochemical reactions associated with the fuel cell technologies. How to reduce Pt usage while maintaining the performance of the catalysts becomes a subject for intensive research in materials chemistry. For heterogeneous catalysis, the catalytic reactivity and selectivity are strongly correlated with different crystallographic facets exposed on the surface. The facets with high-index planes whose Miller indices with at one is larger than unity are generally more active than those with low-index planes (e.g., {100}, {111}, and {110}). Tuning the morphology of the nanoparticles to …

Synthesis Of Bipyridine-Derived Iron Catalysts For Hydrogenation, Jack Elder

Summer Research

Industrially, alkene and carbonyl hydrogenation reactions are catalyzed by iridium, rhodium and ruthenium-centered catalysts. These highly toxic metals are very expensive, both to attain and to dispose of after degradation. This ongoing research seeks to investigate cleaner and more economical alternative catalysts by synthesizing and testing a bipyridine-derived iron catalyst utilizing the unconventional ligand-assisted heterolytic cleavage of hydrogen mechanism to facilitate double bond hydrogenation. In the time allotted, this segment of research sought to synthesize the two catalyst ligands 6-hydroxy-2,2’-bipyrdine and 6,6’-dihydroxy-2,2’-bipyridine, and to model ligand-iron attachment using commercially available iron complexes. The former of the two ligands was synthesized …

Photochemical Oxidation Studies Of Porphyrin Ruthenium Complexes, Eric Vanover

Masters Theses & Specialist Projects

In nature, transition metal containing enzymes display many biologically important, attractive and efficient catalytic oxidation reactions. Many transition metal catalysts have been designed to mimic the predominant oxidation catalysts in nature, namely, the cytochrome P450 enzymes. Ruthenium porphyrin complexes have been the center of this research and have successfully been utilized, as catalysts, in major oxidation reactions, such as the hydroxylation of alkanes. The present work focuses on photocatalytic studies of aerobic oxidation reactions with well characterized ruthenium porphyrin complexes.

The photocatalytic studies of aerobic oxidation reactions of hydrocarbons The photocatalytic studies of aerobic oxidation reactions of hydrocarbons catalyzed by …