Chemical Engineering Commons^™

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

Synthesis, Self-Assembly And High-Pressure Properties Of Nanoparticles And Hybrid Nanocomposites, Lingyao Meng

Nanoscience and Microsystems ETDs

Nanoparticles have gained significant scientific interests owing to their unique structural dimensions, size- and shape-tunable properties, and numerous fascinating applications, from opto-electronics, sensor devices, to energy, environmental, and medical fields. Furthermore, the synergistic integration of other materials, including organic polymers, with nanoparticles provides new opportunities and strategies to obtain nanocomposites with superior properties and functionalities. While there is already significant research on the synthesis and characterizations of nanoparticles and hybrid nanocomposites, some research questions, such as how to design and control the interfacial morphology in polymer/nanoparticle hybrid nanocomposites, how to synthesize metal- organic framework (MOF) nanoparticles in well-defined and uniform …

Investigating The Effects Of Accelerated Lithium Deposition On The Abuse Response Of Lithium-Ion Batteries, Eric J. Deichmann

Chemical and Biological Engineering ETDs

Li deposition at the graphitic anode is widely reported in literature as one of the leading causes of capacity fade in lithium-ion batteries (LIBs). Previous literature has also linked Li deposition resulting from low-temperature and high-rate ageing to diminished safety characteristics, however no current research has probed the effects of Li deposition on the abuse response of well- characterized cells. Additionally, no previous studies have investigated the use of an accelerated Li deposition technique for probing the effects of Li deposition. Using overtemperature testing, a relationship between increased concentrations of Li deposition and exacerbated abuse response in 1Ah pouch cells …

Coulombic And Non-Coulombic Effects Of Single And Overlapping Electric Double Layers With Surface Charge Regulation, Raviteja Vangara

Chemical and Biological Engineering ETDs

The physical origin of charged interfaces involving electrolyte solutions is in the thermodynamic equilibrium between the surface reactive groups and certain dissolved ionic species in the bulk. This equilibrium is very strongly dependent on the precise local density of these species, also known as potential determining ions in the solution. The latter, however, is determined by the overall solution structure, which is dominated by the large number of solvent molecules relative to all solutes. Hence, the solvent contribution to the molecular structure is a crucial factor that determines the properties of electric double layers. Models that explicitly account for the …

An Investigation Of The Chemistry, Thermodynamics And Catalytic Activity Of Molybdenum Carbides, Shanti Kiran Nayak

Chemical and Biological Engineering ETDs

These studies investigate the chemistry and stability of molybdenum carbides as an electrocatalyst. Due to their unique electronic properties, molybdenum carbides are purposed as electrocatalysts for reaction systems such as hydrogen evolution reaction, bifunctional water splitting and CO oxidation.

In this study, various synthesis processes were utilized to produce different types of molybdenum carbide with varying properties of particle size, surface area and excess carbon. The samples characterized by XRD accompanied by Whole Profile Fitting, Electron Microscopy, Gas Adsorption (surface area) and XPS.

These synthesis processes were refined using fundamental thermodynamic analyses. These analyses highlight regions of stability of different …

Symmetry And Dopant Diffusion In Inverted Nanopyramid Arrays For Thin Crystalline Silicon Solar Cells, Seok Jun Han

Chemical and Biological Engineering ETDs

In this dissertation, we enhance the efficiency of thin flexible monocrystalline silicon solar cells by breaking symmetry in light trapping nanostructures and improving homogeneity in dopant concentration profile. These thin cells are potentially less expensive than conventional thick silicon cells by using less silicon material and making the cells more convenient to be handled when supported on polymer films. Moreover, these cells are widely applicable due to their flexibility and lightweight. However, for high efficiencies, these cells require effective light trapping and charge collection. We achieve these in cells based on 14-mm-thick free-standing silicon films with light-trapping arrays of nanopyramidal …

Fluid Transport In Porous Media For Engineering Applications, Eric M. Benner

Chemical and Biological Engineering ETDs

This doctoral dissertation presents three topics in modeling fluid transport through porous media used in engineering applications. The results provide insights into the design of fuel cell components, catalyst and drug delivery particles, and aluminum- based materials. Analytical and computational methods are utilized for the modeling of the systems of interest. Theoretical analysis of capillary-driven transport in porous media show that both geometric and evaporation effects significantly change the time dependent behavior of liquid imbibition and give a steady state flux into the medium. The evaporation–capillary number is significant in determining the time-dependent behavior of capillary flows in porous media. …

Cellular Modification And Artificial Cell Construction, Jimin Guo

Chemical and Biological Engineering ETDs

With all its complexities and different biofunctionalities, a cell is the basic structural and functional unit of all living organisms with the exception of viruses. In this dissertation, I demonstrated gain of function strategies of modifying mammalian cells using silicification and modular nanoparticle (NP) exoskeletons. In addition, I used a modular design concept to build a multifunctional artificial RBC system which can mimic the unique characteristics (e.g. shape, flexibility, the ability to carry oxygen, and long circulation times) of the native RBCs. Together, these cell modification or artificial cell construction strategies are expected to generate new mammalian cell-like structures with …

Metabolon-Inspired Design Of Multi-Modal Catalytic Cascade, Madelaine Seow Chavez

Chemical and Biological Engineering ETDs

Developing hybrid catalytic systems has been researched for the past decade in an effort to efficiently incorporate catalysts of different modalities in catalytic cascades. It has become imperative to design a cascade system where the catalysts are spatially organized to control the delivery of precursors, intermediates, and products. In this work, we have shown that a molecular catalyst, biocatalyst, and metallic catalyst can be co-localized using a carbonaceous support to create a hybrid catalytic system and complete the oxidation of oxalic acid to create a microchemical reactor. The molecular, pyrene-TEMPO catalyst oxidizes glyoxalic acid to oxalic acid. The enzyme oxalate …

Iron-Containing Nanoparticles For The Treatment Of Chrionic Biofilm Infections In Cystic Fibrosis, Leisha M. A. Martin

Nanoscience and Microsystems ETDs

Cystic fibrosis (CF) is the most common genetic disease resulting in the morbidity and mortality of Caucasian children and adults worldwide. Due to a genetic mutation resulting in malfunction of the Cystic Fibrosis Transmembrane Conductance Regulator (CFTR) protein, CF patients produce highly viscous mucus in their respiratory tract. This leads to impairment of the mucociliary clearance of inhaled microbes. In addition to reduced microbial clearance, anoxic environmental conditions in the lungs promote biofilm-mode growth of the pathogenic bacterial species Pseudomonas aeruginosa. Chronic infections of P. aeruginosa begin in early childhood and typically persist until respiratory failure and death result. The …

An Experimental And Numerical Investigation Of Flow Accelerated Flibe Corrosion, David B. Weitzel

Nuclear Engineering ETDs

Renewed interest in molten salt reactor technology has brought to light the need for a better understanding of FLiBe corrosion. To this end a flowing FLiBe corrosion test loop was designed to test the flow effects of FLiBe corrosion. The loop consists of a pump, melt tank, and stainless-steel tubing assembly that heats the molten salt to high temperatures and circulates it over test specimens. The experiment has been constructed and has completed initial shakedown testing.

To support the flowing FLiBe experiment, a numerical corrosion model that couples FLiBe electrochemistry, solid metal diffusion, and mass transport was implemented. The model …

Reaction Of Titanium Subhydride With Multiple Passivating Gasses, Erik C. Strobert Jr

Chemical and Biological Engineering ETDs

Sandia National Laboratories has used substoichiometric titanium hydride as a pyrotechnic fuel for decades. Production of titanium subhydride requires partial dehydriding of titanium hydride powder and subsequent chemical passivation to render the resultant bare titanium surface nonreactive and the powder non-pyrophoric. Novel passivation techniques, using a gas other than air, have been suggested in the past but have never been investigated. This work examines the reaction kinetics of titanium subhydride with three passivating agents, nitrogen, oxygen, and propane. These passivation experiments took place under isothermal conditions (420 ˚C) with varied dehydriding and passivation time periods. It was found that the …

The Endocytotic Fate Of A Mesoporous Silica Nanoparticle Supported Lipid Bylayer Crispr Delivery Vehicle, Angelea Maestas-Olguin

2019 Award Winners

No abstract provided.

Rate-Determining Step And Active Sites Probing For Platinum-Group-Metal Free Cathode Catalyst In Fuel Cell, Yechuan Chen

Chemical and Biological Engineering ETDs

With the increasing demand on renewable energy, the fuel cell has attracted more and more interests because of its large power density and controllable size. However, the insufficiency of element abundance and unstable expensive price of conventional platinum-based electrocatalysts used in anode and cathode makes it essential to find their substitutes. As one of the most promising candidates to be used in cathode for oxygen reduction reaction (ORR), iron-nitrogen-carbon (Fe-N-C) catalysts have been widely investigated and get commercialized recently, but still lacks comprehensive understanding on the kinetic mechanism.

This dissertation has been divided into three parts with a discussion on …

Controlled Nanomorphology Of Hybrid Organic/Inorganic Multi-Component Composites Through Cooperative Non-Covalent Interactions, Lingyao Meng

Shared Knowledge Conference

Hybrid organic–inorganic nanocomposite polymers, with inorganic nanoparticles embedded in organic matrix have emerged as a special category of multifunctional materials. With rational materials design, these hybrids can show the synergistic effect of the properties from both phases. Homogenous dispersion and orderly arrangement of the organic and inorganic components are key in their functionalities. By controlling the interface and corresponding interfacial interactions between the organic and inorganic entities, we have developed a logical approach to form stable and controlled hybrid nanofiber structures. We demonstrate the formation of hybrid polymer/quantum dots (or iron oxide nanoparticles) nanocomposites through non-covalent interactions (hydrogen bonding, ionic …

Spectro-Electrochemical Platforms For Dynamic Analyses Of Catalytic Cascade Systems, Nalin I. Andersen

Nanoscience and Microsystems ETDs

The development of spectro-electrochemical platforms that facilitate the dynamic analyses of complex catalytic cascade systems was explored in this research. These systems facilitated multiple modalities of catalysts and were used as platforms for monitoring catalytic transformations quasi-in situ. The analytical platforms allowed for the characterization of intermediates and products using surface-enhanced Raman spectroscopy (SERS). The design and fabrication of these devices proved to be reproducible, made of materials that can be manipulated for multiple applications, and incorporate fluid mechanics, electrochemistry, and multimodal catalysis. Microfluidic technology offers capabilities for understanding catalytic cascade systems by providing precise dynamic control of …

An Investigation Of The Effects Of The Second Pyrolysis On The Chemistry, Morphology, And Performance Of Iron-Nicarbazin Catalysts, Elizabeth B. Weiler

Chemical and Biological Engineering ETDs

Proton exchange membrane fuel cells offer a cost-effective, environmentally friendly, and sustainable alternative to petroleum-based power sources to the transportation sector. However, slow electrochemical reactions at the cathode of these fuel cell prevent the technology from being competitive. Iron-nitrogen-carbon based catalysts have emerged as a viable answer to this problem, yet further progress is needed to improve their performance beyond that of current state-of-the-art platinum-based catalysts, which are economically and geopolitically impractical to be a final solution. Currently, a two-step high temperature pyrolysis method has proven a promising way to synthesize iron-nitrogen-carbon catalysts for optimized performance, but there is a …

Anodic Catalysts For Anion Exchange Membrane Fuel Cells, Aaron Joseph Roy

Chemical and Biological Engineering ETDs

With a limited availability of energy resources from petroleum and other fossil fuels, as well as growing concerns relating to the environmental implications of fossil fuel emissions, non-carbon fuels which can be utilized in proton and anion exchange membrane fuel cells (PEMFC’s/AEMFC’s), such as hydrogen and hydrazine hydrate (HH), are becoming more attractive as alternative fuels. Historically, platinum and platinum group metal catalysts (PGM) have been used as cathode and anode catalyst materials for both PEMFC’s and AEMFC’s. Although these catalysts are the highest performing catalysts available for the conversion of hydrogen energy in fuel cells, the limited availability and …

Microbial Desalination Cells With Efficient Platinum Group Metal-Free Cathode Catalysts, Morteza Rezaei Talarposhti

Chemical and Biological Engineering ETDs

Iron-nitrogen-carbon based catalyst was used at the cathode of a microbial desalination cell (MDC) and compared with platinum (Pt) and activated carbon (AC) cathode. Fe-N-C catalyst was prepared using nicarbazin (NCB) as organic precursor by sacrificial support method (SSM). Rotating ring disk electrode (RRDE) experiments shows that Fe-NCB had higher electrocatalytic activity compared to AC and Pt. The utilization of Fe-NCB into the cathode improved substantially the performance output with initial maximum power density of 49±2 μWcm^-2 in contrast to Pt and AC catalysts which have shown lower values of 34±1 μWcm^-2 and 23.5±1.5 μWcm^-2, respectively. …

Incorporation Of Catalytic Modalities For Forming Of A Catalytic Cascade, Albert T. Perry Iii

Nanoscience and Microsystems ETDs

This dissertation investigates the novel incorporation of inorganic and enzymatic catalysts. There is little literature on inorganic catalysts operating at biologically relevant pHs and as such a significant amount of this dissertation focuses on determination of catalyst activity. Mn amino-anitpyrene (MnAAPyr), Pt, Pt alloys, Mn-N-C and Pd catalysts on 3D graphene supports(3D-GNS), were explored for activity towards glycerol intermediates: oxalic acid, mesoxalic acid, glyoxalic acid, and formic acid. MnAAPyr was designed to mimic the reaction center of oxalate decarboxylase and oxalate oxidaze, the natural catalyst towards oxalic acid. It showed high activity towards oxalic acid, with onset potentials of 0.714±0.002V …

Ion Size Effects On The Properties Of Charge Regulating Electric Double Layers, Divya Jyoti Prakash

Nanoscience and Microsystems ETDs

The behavior of charged interfaces formed in various systems like colloidal solution, fuel cells, battery, electro-deposition, catalysis is governed by the properties of electrical double layer(EDL). Civilized model with charge regulation boundary condition determined by thermodynamic equilibrium at the interface has been used to model electrical double layer and shows that size of the solvent plays a critical role in characterizing the properties of EDL using classical density functional theory.This thesis investigates the impact of ion size in electrolyte solutions on the electrical double layer formed at the interface using a similar model. It is found that ion size greatly …

Designing Nanocomposite Materials For Catalyzing Electrochemical Reactions In Anion Exchange Membrane Fuel Cells, Sadia Afrin Kabir

Chemical and Biological Engineering ETDs

Fuel cells are considered to be one the most promising sustainable energy technologies for energy conversion and electric power generation. With the development of stable, conductive and high performance anion exchange membranes and ionomers, there has been an increased interest towards studying various electrochemical reactions in Anion Exchange Membrane Fuel Cells (AEMFC). This increased attention has been attributed to the comparatively facile reaction kinetics, minimized corrosion effects and reduced fuel crossover in alkaline media. However, the oxygen reduction reactions (ORR) taking place in the cathode compartment of fuel cells plays a crucial role in optimizing the electrochemical energy conversion efficiency, …

Graphite And Graphene-Oxide Based Pgm-Free Model Catalysts For The Oxygen Reduction Reaction, Joseph Henry Dumont

Nanoscience and Microsystems ETDs

The world currently relies heavily on fossil fuels such as coal, oil, and natural gas for its energy. Fossil fuels are non-renewable, that is, they draw on finite resources that will eventually dwindle, becoming too expensive or too environmentally damaging to retrieve. One alternative source of energy are fuel cells, electrochemical devices that convert chemical energy to cleanly and efficiently produce electricity. They can be used in a wide range of applications, including transportation, stationary, portable and emergency power sources. Their development has been slowed by the high cost of PGM electrocatalysts needed at both electrodes as well as sluggish …

Microdischarges Utilized In Portable Gas Sensing And Their Atmospheric Contaminants, Colin H. Sillerud

Chemical and Biological Engineering ETDs

Portable applications of microdischarges such as the chemical detection, remediation of gaseous wastes, or the destruction of volatile organic compounds will mandate operation in the presence of contaminant species. This work examines the temporal evolution of microdischarge optical and ultraviolet emissions during pulsed operation by experimental methods. By varying the pulse length of a microdischarge initiated in a 4-hole silicon microcavity array operating in a 655 Torr ambient primarily composed of Ne, we were able to measure the emission growth rates for different contaminant species native to the discharge environment as a function of pulse length. It was found that …

Activity Of Pgm-Free Electrocatalysts For Oxygen Reduction Reaction: Ph And Co-Catalysis Effects, Mario Santiago Rojas Carbonell 8148369

Chemical and Biological Engineering ETDs

Fuel cells offer a source to the current and always increasing demand for electric power. But as any new technology, there are challenges that need to be addressed to render it feasible for the market place. One of this challenges is finding the appropriate materials to catalyze the oxygen reduction reaction (ORR) that occurs in the cathode. Oxygen is used as an oxidant in a significant portion of the fuel cells due to its readily availability and high reduction potential. Now, one the bottlenecks that stops the large-scale adoption is the expensive and rare metals that have been used as …

A Study Of Iron-Nitrogen-Carbon Fuel Cell Catalysts: Chemistry – Nanostructure – Performance, Michael J. Workman

Nanoscience and Microsystems ETDs

Fuel cells have the potential to be a pollution-free, low-cost, and energy efficient alternative to the internal combustion engine for transportation and small-scale stationary power applications. The current state of fuel cell technology has already achieved two of these three lofty goals. The remaining barrier to wide-scale deployment is the high cost, which is primarily caused by dependence on large amounts of platinum to catalyze the energy conversion reactions. To overcome this barrier and facilitate the integration of fuel cells into mainstream applications, research into a new class of catalyst materials that do not require platinum is needed.

There has …

Electrochemical Oxidation Of Antibiotic, Antihistamine, Analgesic And Cns Stimulant Pharmaceuticals, Md Mosaddek Hossen

Chemical and Biological Engineering ETDs

Electrochemical oxidation is a common method for the degradation of chemicals by applying potential at a definite value. In this research, ‘cyclic voltammetry’ experiments were conducted to find out the oxidation potential for 8 different pharmaceuticals. Mainly, 3 different pH solutions (pH 6.0, 7.5, 9.0) and 9 different concentrations (1, 2, 5, 10, 20, 50, 100, 200, 500 µM) were studied for each of the pharmaceuticals in this experiments. Acetaminophen, Ibuprofen, Naproxen Sodium, Caffeine showed oxidation peak at 0.34-0.79V, 1.37- 1.39V, 0.94-1.01V, 1.44-1.55V respectively at different pH and concentrations. Antibiotic and antihistamine pharmaceuticals i.e. Erythromycin Hydrate, Triclosan, Sulfanilamide, Diphenhydramine Hydrochloride …

Development Of Metal Matrix Composite Gridlines For Space Photovoltaics, Omar K. Abudayyeh

Chemical and Biological Engineering ETDs

Space vehicles today are primarily powered by multi-junction photovoltaic cells due to their high efficiency and high radiation hardness in the space environment. While multi-junction solar cells provide high efficiency, microcracks develop in the crystalline semiconductor due to a variety of reasons, including: growth defects, film stress due to lattice constant mismatch, and external mechanical stresses introduced during shipping, installation, and operation. These microcracks have the tendency to propagate through the different layers of the semiconductor reaching the metal gridlines of the cell, resulting in electrically isolated areas from the busbar region, ultimately lowering the power output of the cell …

Electrochemical Fabrication Of Energetic Thin Films, Jonathan J. Coleman

Chemical and Biological Engineering ETDs

Current thermal battery heat sources suffer from slow reaction propagation rates and require extreme care when handling to protect from inadvertent ignition sources. Nanostructured intermetallic heat sources are strong candidates for improved heat sources as they have high enthalpy of reaction, are highly conductive before and after firing and are completely gasless reactions. Current fabrication methods of these heat sources rely on a PVD multistep layering process that is time and capital intensive, and cost prohibiting to their use. The composition and nanostructuring these films require can be provided with electrochemical codeposition, where the two components (aluminum and nickel) are …