Chemical Engineering Commons^™

Investigation Of Space Charge Effects On Co2 Electrocatalytic Reduction On Gd-Doped Ceria Via Scanning Kelvin Probe And Model-Based Bayesian Analysis, Alejandro Mejia

Graduate Theses, Dissertations, and Problem Reports

In studying novel energy conversion and storage systems, such as high-temperature electrolysis, numerous underlying fundamental physical processes remain unclear or inadequately understood. Among these, the modeling and comprehension of surface reaction mechanisms, coupled with the intricate effects of space‑charge interfaces, remains an unclear and challenging area of research.

The work of this dissertation involves the development of a 2D finite element analysis model, leveraging the robust MOOSE framework from INL. This model, featuring inhomogeneous defect thermodynamics for near-surface chemistry, formulated through Poisson‑Cahn variational theory, has been exploited for studying the electrocatalytic reduction of CO₂ on gadolinia doped ceria. The …

Synthesis Of Quasi-Freestanding Graphene Films Using Radical Species Formed In Cold Plasmas, Michael A. Mathews Jr.

Graduate Theses, Dissertations, and Problem Reports

For over a decade, the Stinespring laboratory has investigated scalable, plasma assisted synthesis (PAS) methods for the growth of graphene films on silicon carbide (SiC). These typically utilized CF₄-based inductively coupled plasma (ICP) with reactive ion etching (RIE) to selectively etch silicon from the SiC lattice. This yielded a halogenated carbon-rich surface layer which was then annealed to produce the graphene layers. The thickness of the films was controlled by the plasma parameters, and overall, the process was readily scalable to the diameter of the SiC wafer.

The PAS process reproducibly yielded two- to three-layer thick graphene films …

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 …

Thermochemical Water-Splitting Using Novel High-Entropy Perovskite Oxides, Hector Alexis De Santiago Hernandez

Graduate Theses, Dissertations, and Problem Reports

In this project, we designed, synthesized, and tested the transformative (La_0.8Sr_0.2)(Mn_[1-x]/3Fe_[1-x]/3Co_xAl_[1-x]/3)O₃ (0 ≤ x ≤ 1.0) high-entropy perovskite oxides (HEPOs) as redox active oxygen carriers for thermochemical hydrogen production with improved stability, kinetics, and H₂ yield. The developed HEPOs form an R3c (hexagonal) phase and were successfully synthesized using both the Pechini and solid-state reactions with the latter synthesis being the primary source for testing. These innovative perovskites demonstrated an improved kinetics with oxygen surface exchange coefficient, k, greater than 7.5 x 10^-4 cm/s, …

Microwave-Assisted Carbon Nanotube Growth From Methane On Surface Catalyst Exsolving Perovskite Oxide, Angela M. Deibel

Graduate Theses, Dissertations, and Problem Reports

The novel method of using a perovskite exsolution catalyst, strontium titanium nickel oxide (STNO), proved capable of simultaneously producing carbon nanotubes (CNTs) and CO_x-free hydrogen during methane decomposition under microwave irradiation. An optimization of common perovskite materials was conducted for microwave-responsiveness with the results reported in this study. Out of the materials screened, strontium titanium nickel oxide (STNO) was the best candidate to achieve an acceptable methane conversion rate as well as a decent responsiveness to microwave. STNO was further optimized through Ni content, reduction dwell time, and reduction temperature to produce the best methane conversion and CNT …

Calcite Depression In Bastnaesite-Calcite Flotation System Using Organic Acids, Emmy Muhoza

Graduate Theses, Dissertations, and Problem Reports

Bastnaesite is the primary source of light REEs, namely cerium (Ce), lanthanum (La), praseodymium (Pr), neodymium (Nd), to name a few. Bastnaesite is typically concentrated using the froth flotation beneficiation method. Flotation of bastnaesite suffers from high reagent consumption due to the similar surface characteristics of bastnaesite and associated gangue minerals, including calcite. Additionally, complex stages of high-temperature conditioning are often required to suppress the detrimental impact of dissolved calcium ions on the flotation of bastnaesite. This research seeks to investigate the capabilities of organic acids in the bastnaesite-calcite flotation systems to selectively depress calcite minerals and effectively chelate calcium …

Combinatorial Approaches For Effective Design, Synthesis, And Optimization Of Enzyme-Based Conjugates, Jordan Scott Chapman

Graduate Theses, Dissertations, and Problem Reports

The specificity and efficiency with which enzymes catalyze selective chemical reactions far exceeds the performance of traditional heterogeneous catalysts that are predominant in industrial applications such as conversion of commodity chemicals to value-added products, fuel cells, and petroleum refinement. Moreover, biocatalysts exhibit exceptionally high product turnover at ambient conditions with little health and environmental burden. These advantageous qualities have led to the prolific use of enzyme catalysis in pharmaceutical, detergents, and food preservation industries wherein their use has greatly reduced waste generation, Unfortunately, the full slate of benefits that enzymes can impart to a broader range of chemical processes is …

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 …

Improving Performance And Durability Of Intermediate Temperature Proton‐Conducting Solid Oxide Electrolysis Cells Via Materials Design And Catalyst Surface Engineering, Hanchen Tian

Graduate Theses, Dissertations, and Problem Reports

Solid oxide steam electrolysis cell, a promising electrical-chemical conversion device for the next generation efficient hydrogen production and energy storage, has been actively studied because of their high energy conversion efficiencies and prospective applications as electrochemical reactors. After decades of research on protonic ceramic materials, remarkable advances have been made in the protonic ceramic electrochemical cells (PCECs) air electrode and electrolyte. However, the existing air electrodes are far from satisfying the requirements of practical applications, a series of issues, including the lack of active and durable electrodes, greatly limit the commercialization. To date, the systematic development of triple conducting catalysts …

Dry Reforming Of Methane Using Microwave Irradiated Metal Oxide/Coal Char Catalysts, Anthony Carter

Graduate Theses, Dissertations, and Problem Reports

This research focuses on the synthesis of both shaped and amorphous powder materials, the combination of these materials with dried Powder River Basin (PRB) coal char, and their reactionary properties with methane and carbon dioxide gasses with conventional and microwave (MW) heating. The first goal of this project was to synthesize shaped micro and nano sized particles with ideal dielectric properties for converting electromagnetic energy into heat and proven capabilities of activating methane. These particles were synthesized via solvothermal, hydrothermal, and co-preceptory treatments alone and onto the surface of dried PRB coal char. PRB is a sub-bituminous, low-ranking coal (LRC) …

Synthesis Of Graphene Using Plasma Etching And Atmospheric Pressure Annealing: Process And Sensor Development, Andrew Robert Graves

Graduate Theses, Dissertations, and Problem Reports

Having been theorized in 1947, it was not until 2004 that graphene was first isolated. In the years since its isolation, graphene has been the subject of intense, world-wide study due to its incredibly diverse array of useful properties. Even though many billions of dollars have been spent on its development, graphene has yet to break out of the laboratory and penetrate mainstream industrial applications markets. This is because graphene faces a ‘grand challenge.’ Simply put, there is currently no method of manufacturing high-quality graphene on the industrial scale. This grand challenge looms particularly large for electronic applications where the …

Time-Dependent Reliability Framework For Durability Design Of Frp Composites, Rajneesh Kumar Bharil

Graduate Theses, Dissertations, and Problem Reports

The life-cycle performance, durability, and aging characteristics of Fiber Reinforced Polymer (FRP or Structural Composites) have been of keen interest to the engineers engaged in the FRP design, construction, and manufacturing. Unlike conventional construction materials such as steel and concrete, the design guidelines to account for the aging of FRP are somewhat scattered or not available in an approved or consistent format. Loss of strength over time or aging of any structural material should be of concern to engineers as the in-service lifespan of many engineering structures is expected to exceed 100 years. Use of durability strength-reduction factors or factors …