Catalysis and Reaction Engineering Commons^™

Microplate-Like Metal Pyrophosphate Engineered On Ni-Foam Towards Multifunctional Electrode Material For Energy Conversion And Storage, Rishabh Srivastava

Electronic Theses & Dissertations

High clean energy demand, dire need for sustainable development, and low carbon footprints are the few intuitive challenges, leading researchers to aim for research and development for high-performance energy devices. The development of materials used in energy devices is currently focused on enhancing the performance, electronic properties, and durability of devices. Tunning the attributes of transition metals using pyrophosphate (P₂O₇) ligand moieties can be a promising approach to meet the requirements of energy devices such as water electrolyzers and supercapacitors, although such a material’s configuration is rarely exposed for this purpose of study.

Herein, we grow …

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 …

From Waste To Energy: The Electrochemical Reduction Of Co2 Using Recycled Nanostructured Catalysts, Ibrahim Badawy

Theses and Dissertations

The reduction of carbon dioxide (CO₂RR) using electrochemistry is a promising solution for the burgeoning global energy crisis. The overall vision of its implementation relies on renewable energy sources to power the reaction creating carbon neutral products and effectively closing the carbon cycle. Research in this field has come a long way since its inception in the mid-1900s. However, there remain significant hurdles and important considerations to overcome in order to reach full commercialization. Most electrocatalysts tested for CO₂RR have been designed solely for maximum performance while ignoring the environmental consequences if such a material were …

The Study Of Corrosion On Additive-Manufactured Metals., Braydan Daniels

Electronic Theses and Dissertations

The purpose of this study was to investigate and compare the corrosion mechanisms between wrought and additive-manufactured (3D-printed) copper and stainless steel. The experimental procedure consisted of measuring the open circuit potential, electrochemical impedance spectroscopy, linear sweep voltammetry, Tafel analysis, surface topology, and scanning electron microscopy for each metal within salt water, tap water, sulfuric acid, and synthetic body fluid (excluding copper in synthetic body fluid).

Overall, printed stainless steel was more corrosion-resistant than wrought stainless steel in tap water and synthetic body fluid based on OCP, LSV, and surface topology results. Additionally, printed copper was more corrosion-resistant than wrought …

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 …

Elucidation Of Active Site And Mechanism Of Metal Catalysts Supported In Nu-1000, Hafeera Shabbir

All Dissertations

Advances in extraction of shale oil and gas has increased the production of geographically stranded natural gas (primarily consisting of methane (C1) and ethane (C2)) that is burned on site. A potential utilization strategy for shale gas is to convert it into fuel range hydrocarbons by catalytic dehydrogenation followed by oligomerization by direct efficient catalysts. This work focuses on understanding metal cation catalysts supported on metal-organic framework (MOF) NU-1000 that will actively and selectively do this transformation under mild reaction conditions, while remaining stable to deactivation (via metal agglomeration or sintering). I built computational models validated by experimental methods to …

Intersections Of Environmentalism, Chemistry, And Racism: An Experimental Study Of Halobenzene Hydrogenolysis And Critical Communication Studies Of Equitable Learning Practices Rooted In Black Feminism, Lauren O. Babb

Electronic Theses and Dissertations

Increasing concentrations of fluorinated aromatic compounds in surface water, groundwater, and soil pose threats to the environment. Fundamental studies that elucidate mechanisms of dehalogenation for C-X compounds (where X represents a halide) are required to develop effective remediation strategies. For halogenated benzenes, previously published research has suggested that the strength of the C-X bond is not rate-determining in the overall rate of dehalogenation. Instead, the rate-determining step has been hypothesized to be adsorption of the C-X compound onto the surface of a catalyst. Building on this hypothesis, in this work, we examine the reaction kinetics of fluorobenzene conversion to benzene, …

Chromatographic Dynamic Chemisorption, Shreya Thakkar

Masters Theses

Reaction rates of catalytic cycles over supported metal catalysts are normalized by the exposed metal atoms on the catalyst surface, reported as site time yields which provide a rigorous standard to compare distinct metal surfaces. Defined as the fraction of exposed metal surface atoms to the total number of metal atoms, it is important to measure the dispersion of supported metal catalysts to report standardized rates for kinetic investigations. Multiple characterization techniques such as electron microscopy, spectroscopy and chemisorption are exploited for catalyst dispersion measurements. While effective, electron microscopy and spectroscopy are not readily accessible due to cost and maintenance …

Photocatalytic Degradation Of Organic Contaminants By Titania Particles Produced By Flame Spray Pyrolysis, Noah Babik

Theses and Dissertations

Advanced oxidation of organic pollutants with TiO2 photocatalysts is limited due to the wide bandgap of TiO2, 3.2 eV, which requires ultraviolet (UV) radiation. When nanosized TiO2 is modified by carbon doping, charge recombination is inhibited and the bandgap is narrowed, allowing for efficient photodegradation under visible light. Here, we propose a flame spray pyrolysis (FSP) technique to create TiO2. The facile process of FSP has been successful in preparing highly crystalline TiO2 nanoparticles. Using the same procedure to deposit TiO2 onto biochar, the photocatalyst was doped by the carbonaceous material. The morphology, crystalline and electronic structure of the FSP …

Structural, Charge Transport, Gas Sensing, Magnetic, Pseudocapacitive, And Electrocatalytic Properties Of Perovskite Oxides., Surendra Bahadur Karki

Electronic Theses and Dissertations

Perovskites are functional materials with the general formula ABO₃ (A = alkali, alkaline earth or lanthanoid cations and B = transition metal or main group cations). These materials are marked by a variety of crystal structures and interesting properties such as colossal magnetoresistance, ferroelectricity, multiferroicity, superconductivity, pseudocapacitance, gas sensing, charge transport, and electrocatalytic properties. The formula of perovskite can be written as AA’BB’O₆, when there is ordering between two cations over A and B-sites. Such compounds are called double perovskite oxides. Some amount of oxygen could be lost from crystal structure without decomposition of the phase. Such …

Computational Study Of The Reactions Of Heteroatomic Compounds On Ceo2, Suman Bhasker Ranganath

LSU Doctoral Dissertations

The mechanisms of ambient-temperature reactions of heteroatomic compounds catalyzed by ceria (CeO₂), an archetypical reducible oxide, for enzyme mimetics, environmental protection, and chemical synthesis are investigated in this dissertation using theoretical methods. CeO₂ is modeled with thermodynamically stable low-index surfaces exposed by commonly studied ceria thin films and nano particles. To understand phosphatase-like dephosphorylation activity, stable adsorption states and surface reactions of model phosphates are examined. Binding of the central P-atom to surface lattice oxygen (O_latt) supplemented by phosphoryl O-Ce interaction is the only stable adsorption state for the un-dissociated molecule. Deprotonation of phosphate monoesters, …

Design And Fabrication Of Nanostructured Electrodes For Complementary Electrochemical And Photoelectrochemical Water Splitting, Kholoud El Sayed Abousalem

Theses and Dissertations

Designing highly active, durable, and nonprecious electrodes for overall water splitting is of urgent scientific importance to realize sustainable hydrogen production. Accordingly, the need to search efficient energy production systems is of crucial necessity. In this thesis, two various systems for sustainable hydrogen production have been reported using electrochemical and photoelectrochemical pathways. In the first part of the thesis, electrochemical water splitting involving both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) has been established. To this end, an innovative approach is demonstrated to synthesize flower-like 3D homogenous trimetallic Mn, Ni, Co phosphide catalysts directly on nickel foam via …

Photocatalytic Degradation Of Lignin By Supported Silver Nanoparticles, Ning Wei

Theses and Dissertations--Chemical and Materials Engineering

Lignin is the second most abundant form of biomass on earth. The phenolic structure and high carbon to oxygen ratio make lignin an attractive renewable source of fuel and chemicals. However, its recalcitrance and heterogeneous nature prove difficult for decomposing lignin’s polymer structure and separation of the products. This work has focused on the use of low-energy catalytic approaches to overcome these barriers. A mimic of the lignin degrading enzyme laccase, consisting of a copper cluster Cu4Py4I4 modified with AgNO3, was developed to function similarly to the laccase active site. The prepared copper complex solution was found to be active …

Scale-Up Of Flow-Electrode Capacitive Deionization Method For Hard Water Softening, Noah Henry

Williams Honors College, Honors Research Projects

This study’s purpose is to further document a capacitive deionization design that could be capable of purifying H₂O at a household scale where clean water is otherwise unobtainable in applicable regions of the world. The hypothesis behind this study was continuously larger scaled electrochemical cell-units would increase their water softening capabilities in sustainable fashion. The trend at which performance will scale is currently unknown. The units studied were constructed using graphite plates, anion exchange membranes, cation exchange membranes, and Teflon channels. Three streams, two being CaCl₂ solutions in DI H₂O (one being concentrated with CaCl …

Development Of Density-Functional Tight-Binding Methods For Chemical Energy Science, Quan Vuong

Doctoral Dissertations

Density-functional tight-binding (DFTB) method is an approximation to the popular first-principles density functional theory (DFT) method. Recently, DFTB has gained considerable visibility due to its inexpensive computational requirements that confer it the capability of sustaining long-timescale reactive molecular dynamics (MD) simulations while providing an explicit description of electronic structure at all time steps. This capability allows the description of bond formation and breaking processes, as well as charge polarization and charge transfer phenomena, with accuracy and transferability beyond comparable classical reactive force fields. It has thus been employed successfully in the simulation of many complex chemical processes. However, its applications …

Electrochemical Deposition In Energy Storage Devices, Witness Atutala Martin

Graduate Theses and Dissertations

Metals, whether in a solid or soluble ion form, are a vital part of any electrochemical storage system. More so, Li metal is widely considered as the ideal anode because of its low density and low electrochemical potential (-3.04 V vs. the standard hydrogen electrode – SHE). However, just like most metals, it does not plate or strip evenly during cycling which can lead to cycling performance issues, short cycling lifespans, and even safety concerns brought about by dendrites that can cause internal short-circuiting within cells. This research focused on investigating the electroplating of metals in both aqueous and non-aqueous …

Investigative Study Of Microalgal And Electrochemical Wastewater Treatment Systems And Modeling Of The Wafer-Enhanced Electrodeionization Using Supervised Learning, Humeyra Betul Ulusoy Erol

Graduate Theses and Dissertations

Wastewater has a serious impact on environment and public health due to its high concentration of nutrients and toxic contaminants. Without proper treatment, excess nutrients discharged in wastewater can cause a damage to the ecosystem such as undesirable pH shifts, cyanotoxin production, and low dissolved oxygen concentrations.

Main objectives of this dissertation work were to investigate i) the biofuel potential of P. cruentum when grown in swine wastewater, ii) the influence of four most commonly used ion exchange resins on the system efficiency and selectivity for the removal of sodium, calcium, and magnesium ions, and iii) the modeling of wafer-enhanced …

Valorization Of Xylan In Agroforestry Waste Streams, Harrison Appiah

Graduate Theses, Dissertations, and Problem Reports

Valorization of Xylan in Agroforestry Waste Streams.

Harrison Appiah

Microwave-assisted deep eutectic solvent and gamma-valerolactone metallic chloride catalyzed conversion of xylan to furfural were investigated using a 2x3 factorial experimental design at two levels of percent microwave power, reaction time, and catalyst concentration. The levels of each factor studied were (20%, 60% microwave power, 2, 4 minutes, and 10, 20mg) respectively. The effect of three metallic chloride catalysts (LiCl, FeCl3.6H20, CuCl2) on the conversion of xylan to furfural was also investigated. The gamma-valerolactone-ferric chloride sent system exhibited the highest mean yield of furfural (56.50%). The next highest furfural yield of …

Understanding Biomass Upgrading Through Hydrogenolysis Reactions: Kinetics And Mechanism, Jalal Tavana

Electronic Theses and Dissertations

This dissertation involves several hydrogenolysis reactions but is mainly focused on hydrodechlorination (HDC) of chlorobenzene (PhCl) and hydrodeoxygenation (HDO) of 2-furancarboxylic acid (FCA). Hydrodechlorination of PhCl has been the subject of research for some time. Here, we used a Pd/C catalyst to study this reaction though rigorous kinetics and mechanistic analyses in a CSTR reactor. The H₂/D₂ kinetic isotope effect (KIE) experiment revealed that H₂ is not involved in a rate controlling step. The kinetics data are in agreement with similar systems reported before and follow a first-order dependence on chlorobenzene, half order for hydrogen and …

Understanding The Role Of Atom Trapping In The Evolution Of Hydrocarbon Transformation Catalyst Morphology, Griffin Canning

Chemistry and Chemical Biology ETDs

Converting alkanes to other, more chemically and economically valuable molecules requires catalysts that can survive elevated temperatures and highly reducing environments. These environments can cause many metal-nanoparticle based catalysts to sinter rapidly, causing a loss of activity. They must also tolerate the coke formation, as well, since coke can restrict access to active sites by gas phase molecules, thus lowering catalytic activity. While there are routes to improve both the sinter and coke resistance of catalysts, an alternative strategy is to develop a protocol for regenerating the activity of the catalyst in question when coke formation or sintering becomes problematic. …

Atom Trapping And Its Role On The Nucleation & Growth Of Platinum Nanoparticles, Deepak Kunwar

Chemistry and Chemical Biology ETDs

Diesel oxidation catalysts deactivate due to Pt sintering, a major problem in automotive industries. To make sure they operate effectively throughout the lifetime of the vehicle, automotive industries are putting an excessive amount of Pt. There is a need to develop a catalyst that serves long term performance with minimal use of Pt. Jones et al^.1 demonstrated that ceria traps Pt atoms. His work generated some logical and valid questions such as what is the mechanism for the formation of anomalously large Pt particles? What is the upper limit of Pt metal loading in the form of single atoms …

Effect Of Cocatalyst Combination In Titanium-Based Ziegler-Natta Catalyst On Olefin Polymerization, Thanyaporn Pongchan

Chulalongkorn University Theses and Dissertations (Chula ETD)

This research focused on effect of cocatalyst types (TEA, TnOA, and TEA+TnOA) on titanium-based Ziegler-Natta catalyst in olefin polymerization both in slurry and gas-phase systems. This study has been divided into four sections. The commercial titanium-based catalyst was selected to investigate effect of reaction temperature and oxidation state of titanium from ESR measurement on slurry ethylene and propylene polymerization in the first and the second parts, respectively. The commercial catalyst with TEA exhibited the highest activity in ethylene polymerization. However, divalent, and trivalent of titanium (Ti2+ and Ti3+) was active in ethylene polymerization to produce more polymer. Stability of Ti3+ …

Quantitative Probing Of Vacancies And Ions Dynamics In Electroactive Oxide Materials, Jiaxin Zhu

Doctoral Dissertations

Oxygen vacancy and ion dynamics in functional oxides are critical factors influencing electrical conductivity and electrochemical activity of oxides assemblies. The recent advancements in deposition and fabrication of oxide heterostructured films with atomic-level precision has led to discovery of intriguing physical properties and new artificial materials. While still under debate, researchers most often attribute these observed behaviors to unique oxygen vacancy distributions in the substrate near heterointerfaces. In electroactive oxides devices such as solid oxide cells (SOCs), oxygen vacancy and ion transport at the triple-phase boundary determines the performance of the device. This complex process motivates numerous remaining questions regarding …

Synthesis And Molecular Transport Studies In Zeolites And Nanoporous Membranes, Vivek Vattipalli

Doctoral Dissertations

The advent of nanoporous materials such as zeolites and nanoporous membranes has provided cost-effective solutions to some of the most pressing problems of the 20^th century such as the conversion of crude oil into fuels and valuable chemicals. Hierarchical zeolites and mesoporous inorganic membranes are showing great promise in addressing new problems such as the conversion of biomass into value-added chemicals and development of energy-efficient separation processes. The synthesis and fundamental aspects of molecular transport in these new materials with hierarchical porosities need to be better understood in order to rationally develop them for these desired applications. Pore narrowing …

Towards Sustainable Production Of Chemicals And Fuels From The Fast Pyrolysis Of Waste Polyolefin Plastics, Ulises Gracida Alvarez

Dissertations, Master's Theses and Master's Reports

The increasing amount of plastic waste (PW) generation has become an important concern due to the leveled-off recycling rates. Therefore, governmental agencies around the world, including state governments in the United States, have proposed initiatives to minimize the amount of PW that is landfilled and encourage recycling or energy recovery. Circular economy is a strategy that attempts on reusing PW to produce new polymers while avoiding its disposal and the use of virgin material. Chemical recycling raises an interesting technology prospect due to the potential reduction of pollutant emissions and the establishment of a circular economy through the production of …

Mechanistic Studies Of Reducible Metal Oxides As Hydrodeoxygenation Catalysts, Akbar Mahdavi Shakib

Electronic Theses and Dissertations

Hydrodeoxygenation of phenol to benzene using ruthenium supported titania catalysts strongly varies depending on the support crystal structure and preparation conditions. Here, we performed spectroscopic characterization of titania supports to identify the surface impurities common to commercial and synthesized titania samples using a variety of spectroscopic methods. Sulfate impurities were detected for the commercial anatase samples and a procedure for their elimination was proposed so that inactive catalysts gained reactivity. Surface hydroxyls of different TiO2 samples (anatase, rutile, and pyrogenic) were identified using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments performed on vigorously cleaned surfaces and a facet-specific assignment …

Nanoporous Carbon-Based Co2 Reduction Catalysts: Exploring The Combined Effects Of Surface Chemistry And Porosity, Wanlu Li

Dissertations, Theses, and Capstone Projects

For the first-time sulfur-doped, nitrogen-doped and sulfur, nitrogen-codoped nanoporous carbons were systematically studied as catalysts for CO₂ electrochemical reduction reaction (CO₂ERR). The Faradaic efficiencies (FE) of CO and CH₄ formation were calculated to evaluate the performance of these carbons. The best catalysts showed the FE of CO and CH₄ formation of 29% and 0.76%, respectively. It was found that the overall performance in CO₂ERR dramatically increased upon the reduction pretreatment of the carbons in N₂-saturated electrolyte before the CO₂ reduction process. The pretreated carbon showed the maximum FE of CO …

An Application Of M-Matrices To Preserve Bounded Positive Solutions To The Evolution Equations Of Biofilm Models, Richard S. Landry Jr.

University of New Orleans Theses and Dissertations

In this work, we design a linear, two step implicit finite difference method to approximate the solutions of a biological system that describes the interaction between a microbial colony and a surrounding substrate. Three separate models are analyzed, all of which can be described as systems of partial differential equations (PDE)s with nonlinear diffusion and reaction, where the biological colony grows and decays based on the substrate bioavailability. The systems under investigation are all complex models describing the dynamics of biological films. In view of the difficulties to calculate analytical solutions of the models, we design here a numerical technique …

Fabrication And Modification Of Titania Nanotube Arrays For Harvesting Solar Energy And Drug Delivery Applications, Ahmed El Ruby Abdel Rahman Mohamed

Electronic Thesis and Dissertation Repository

The fast diminishing of fossil fuels in the near future, as well as the global warming caused by increasing greenhouse gases have motivated the urgent quest to develop advanced materials as cost-effective photoanodes for solar light harvesting and many other photocatalytic applications. Recently, titania nanotube arrays (TNTAs) fabricated by anodization process has attracted great interest due to their excellent properties such as: high surface area, vertically oriented, highly organized, one-dimensional, nanotubular structure, photoactivity, chemical stability and biocompatibility. This unique combination of excellent properties makes TNTAs an excellent photoanode for solar light harvesting. However, the relatively wide band gap energy of …

An Exploration Of Basic Processes For Aqueous Electrochemical Production Of Hydrogen From Biomass Derived Molecules, Brian Fane

Doctoral Dissertations

Polymer electrolyte membrane fuel cells(PEMFCs) are energy conversion devices with significant potential. The factors preventing them from becoming widespread concern production and distribution of hydrogen. Developing an efficient hydrogen infrastructure with an approachable rollout plan is an essential step towards the future of fuel cells. Water electrolysis is limited by the thermodynamics of the process, which leads to high electrical consumption and significant materials challenges. Alternative methods for cleanly generating hydrogen while using a lower cell voltage are required. PEM based electrolyzers can operate with a "depolarized anode", whereby they become significantly less power hungry.

This thesis explores two techniques …