Chemical Engineering Commons^™

Computational Design Of Electro-Organocatalysts And Transition Metal Sulfides For The Electrochemical Reduction Of Co2, Foroogh Khezeli

LSU Doctoral Dissertations

Abstract

Electrochemical CO₂ reduction (ECO₂RR) has emerged as a promising approach for generating carbon-neutral liquid fuels by utilizing excess renewable electricity to convert CO₂. This thesis aims to employ atomistic simulations by using Density Functional Theory (DFT) to investigate the mechanistic details of how transition metal sulfides and electro-organocatalysts can enhance the activity and selectivity towards desired products, including those containing C-H bonds and molecules with C-C bonds. For this project, three different electrocatalysts were designed computationally.

Firstly, MoS₂ was chosen as a transition metal sulfide catalyst with the objective of understanding the kinetics …

Design And Synthesis Of Plasmonic Nanoparticles For Nir Bioimaging: Investigating The Role Of Absorption And Scattering, Luis Dias Bumba Manuel

LSU Doctoral Dissertations

Nanoparticles have made vast advances in the realm of nanomedicine and bioimaging, enabling technologies such as photothermal therapy of malignant tumors and noninvasive monitoring of living tissue. Many of these innovations have only arisen in the last few decades with potential for growth in many avenues. The research shown in this work addresses some of the existing literature's void. Particularly solving synthesis challenges that have existed for more than 20 years in synthesizing Au nanoshells and establishing the potential for molecular-level deep imaging of plants. A novel investigation of the role of light absorption and scattering in bioimaging led to …

Improved Selectivity And Stability In Methane Dry Reforming By Atomic Layer Deposition Onto Ni-Ceo2-Zro2/Al2o3 Catalysts, Jonathan Lucas

LSU Master's Theses

The use of Ni in the dry reforming of methane (DRM) has been widely studied as a replacement for noble metal catalysts (Pt, Pd, Rh) due to Ni’s low cost compared to noble metals, its abundance, and the fact that its DRM activity is near that of noble metal catalysts. However, Ni has been shown to deactivate quickly under DRM conditions. Rare earth oxides such as CeO₂, or as CeO₂-ZrO₂ (CZO) are supports that improve both the activity and stability of Ni DRM systems due to their redox activity. However, this same activity is thought …

A Data-Driven Multivariate Process Monitoring Platform For Knowledge Discovery And Model Building In Industrial Applications, Estelle E. Seghers

LSU Master's Theses

In industrial chemical manufacturing processes, the amount of raw data generated can add complexity in the analysis and understanding of the process dynamics. Being able to properly interpret this data can help improve plant operation, especially regarding safety and profitability. This research has culminated in FastMan-JMP, a platform proposed for monitoring of industrial processes and optimization of the offline data-driven model-building process as part of the process monitoring workflow. FastMan-JMP is a tool developed in Python to apply various data mining and machine learning techniques quickly and easily to better understand valuable patterns and hidden trends in process data. One …

Hybrid Modeling For Electrochemical Systems, Luis Alejandro Briceno-Mena

LSU Doctoral Dissertations

The discovery of new materials like catalysts, polymeric films, and biomolecules, is driven by industrial needs such as improving reaction or separation selectivity, enhancing therapeutic effects on medical treatments, or reducing costs of replacement. However, deployment of these advances in industrial applications is often hindered by the lack of models needed for design and optimization. Due to the novelty of materials and devices, experimental data and first principles' knowledge are scarce, making it hard to build models either via data-driven or knowledge based approaches. In this context, a way to efficiently combine domain knowledge with data could provide a pathway …

Non-Equilibrium Colloidal Phenomena In Magnetic Fields And Photoillumination: From Controlling Living Microbots To Understanding Microplastics, Ahmed Al Harraq

LSU Doctoral Dissertations

Colloids are a ubiquitous class of materials composed of microscopic particles suspended in a continuous phase which are found in everyday products and in nature. Colloids are also useful models for studying the spontaneous arrangement of matter from individual building blocks to mesophases. Standard treatment of colloid science is based on the assumption of equilibrium conditions, as defined in traditional thermodynamics. However, novel assembly mechanisms and motility are unlocked by pushing colloids away from equilibrium using external energy. In addition, many colloids in nature and in industrial applications exchange energy and mass with the surrounding environment thus behaving in a …

Computational Study Of C-C Coupling Reactions On Heterogeneous Catalysts, Md Saeedur Rahman

LSU Doctoral Dissertations

The utilization of carbon dioxide (CO₂) in chemical production has attracted global research interest. Reacting CO₂ with methane (CH₄) removes these greenhouse gases from the atmosphere and turns both compounds into building blocks for organic compound synthesis. A commonly explored pathway involves dry reforming of methane (DRM), which reacts CH₄ and CO₂ to form syngas, a mixture of H₂ and CO. Syngas is a widely used feedstock for synthesizing chemicals ranging from methanol to fuels via the Fischer-Tropsch (FT) process. However, DRM has a large positive ΔGº, which requires the …

Application Of Distributed Fiber-Optic Sensing For Pressure Predictions And Multiphase Flow Characterization, Gerald Kelechi Ekechukwu

LSU Doctoral Dissertations

In the oil and gas industry, distributed fiber optics sensing (DFOS) has the potential to revolutionize well and reservoir surveillance applications. Using fiber optic sensors is becoming increasingly common because of its chemically passive and non-magnetic interference properties, the possibility of flexible installations that could be behind the casing, on the tubing, or run on wireline, as well as the potential for densely distributed measurements along the entire length of the fiber. The main objectives of my research are to develop and demonstrate novel signal processing and machine learning computational techniques and workflows on DFOS data for a variety of …

Programming The Properties Of Branched Polymers Through Precision Architectures, Michael R. Dearman

LSU Master's Theses

The glass transition of branched polymers is determined by multiple structural parameters that dictate their inter- and intramolecular interactions, and ultimately, their molecular packing in the amorphous phase. Here we examined the impact of side chain length, backbone length, molecular weight composition, and topology on the glass transition behavior of bottlebrush polymers. Through examining precision bottlebrush polymer libraries (PBP, ĐSC = 1.0), we find the infinite molecular weight Tg is reached at a specific brush length after which the effect of the side-chain length dominates. Being a factor more dominant than the backbone, side-chain length affects the Tg of bottlebrush …

Comparison Of Two Capital Cost Assessment Methods For A Styrene Process Design, Marian K. Luzier

Honors Capstones

No abstract provided.

Phase Transitions And Photoluminescent Properties Of Anion-Engineered Y2o3, Maharram Jabrayilov

LSU Master's Theses

Rare earth doped metal oxides are widely employed as phosphor materials for white light LEDs (w-LEDs). The aim of this work is to engineer anionic sites of metal oxides, specifically, Y₂O₃, to investigate structural and luminescent properties relationships and energy transfer mechanisms between rare earth sensitizer and activator ions in different hosts.

A low temperature two-step hydrothermal/combustion method was employed to incorporate sulfate ions into Y₂O₃. Furthermore, annealing at 600 °C under H₂/N₂ was employed to convert Y₂O₂SO₄ to Y₂O₂S. …

Ultraviolet Chiral Plasmonics, Tiago Ramos Leite Da Silva

LSU Doctoral Dissertations

The far- (λ < 250 nm) ultraviolet (UV) chiroptical response from protein secondary structures can aid in understanding protein interactions for drug discovery. Chiral metasurfaces have attracted attention to enhance the intrinsically weak biomolecular optical activity for improved structural biology characterization. However, due to materials and fabrication challenges, current metasurfaces mostly operate in the visible and near-infrared regimes with limited, if any, response in far-UV. The large spectral mismatch between metasurface and biomolecular resonances limits the chiral enhancement factor. In this work, we study aluminum planar metamaterials which display optical activity in the UV region. In the first part of this work, we experimentally and computationally investigate the resonant plasmonic-biomolecular interactions in the far-UV. To the best of our knowledge, our work is the first to experimentally explore these resonant interactions in the biologically relevant far-UV regime. We demonstrate experimentally and computationally enhanced chiral sensing of sub-10 nm amino acid films. We develop a full-wave computational model of a biomolecular film on an aluminum gammadion array using experimentally derived chiral parameters (κ) for L- and DTyrosine films. Our model shows that detectable enhancements in the circular dichroism (CD) and birefringence (CB) signals from small amounts of biomolecules are only possible when tight spectral overlap exists between the plasmonic and biomolecular chiroptical signals. We support this conclusion experimentally by fabricating aluminum gammadion arrays on fused silica substrates and sublimating ultrathin racemic, L- and D- Tyrosine films on the arrays. Complete Mueller matrix analysis of the resonant plasmonic-biomolecular system agrees with our computational results and demonstrates the importance of using far-UV active metasurfaces for enhancing natural optical activity. In the second part of this work, we study hybrid aluminum reflective metasurfaces, which leverage both local and propagating surface plasmons (PSP). These materials display strong bi-anisotropy with rich polarization conversion properties. We explore several geometries and verify how their symmetry properties affect their far-field response. Our observations provide an opportunity for researchers to improve the chiral response of plasmonic metasurfaces, especially in the challenging ultraviolet regime.

Electric Field Driven Co-Assembly And Transport Of Colloids Using Active-Passive Interaction, Brishty Deb Choudhury

LSU Master's Theses

Over the past few decades, the out-of-equilibrium transport and assembly of colloidal particles have been drawing significant interest due to their myriad applications in biology, engineering, and physics. In the absence of any external force, micro and nanoparticles perform Brownian motion in dispersion and are termed as passive colloids. In contrast, active colloids are a class of particles where a net imbalance of fluid flow around their surface drives their net migration in space when subjected to an external electric field. While several studies have shown the ability to program the dynamics of active colloids using an external electric field, …

Bioremediation Of Petroleum-Based Contaminants By Alkane-Degrading Bacterium Alcanivorax Borkumensis, Amber Julaine Pete

LSU Doctoral Dissertations

The world’s dependence on petroleum hydrocarbons has led to significant environmental implications. For example, oil spills cause lasting environmental damage, and the increase of plastics in the marine environment has been growing, specifically, microplastics that can be difficult to detect due to their small size. Petroleum hydrocarbons occur naturally in nearly all marine environments, which has allowed hundreds of microorganisms to evolve to utilize these hydrocarbons as their primary energy source. These microbes are classified as hydrocarbonoclastic and are utilized to remove spilled oil biodegradation. Over the last ten years, progress has been made in the biodegradation of oil spills …

Scale Up Of A Novel Method To Maximize Malonyl-Coa In Escherichia Coli, Clifford Harris Leblanc Iv

LSU Master's Theses

The instability of oil’s price along with its limited availability and impact on the environment motivate the search for an alternative feedstock that can sustain the profitability of chemical companies. Industrial biotechnology can promote renewable sources of energy and products by using microorganisms to produce a wide range of chemical compounds. The three-carbon metabolite, malonyl-CoA, can serve as a precursor to a variety of industrial chemicals. The major hurdle with using malonyl-CoA in industry is that its intracellular concentration in Escherichia Coli is very low. Previous attempts to increase the intracellular level of malonyl-CoA have ranged from genetic engineering of …

Engineering The Lanthanide And Actinide Dopants Effects On The Local Environment Of Luminescent Complex Metal Oxide, Yuming Wang

LSU Doctoral Dissertations

Rare earth (RE) based phosphor materials are widely used as luminescent probes in high-temperature optical thermometry where standard methods are unsuitable. The current generation of luminescent thermometers lacks stability and energy transport within the operating temperature ranges. The challenge is developing an oxide-based material with high luminescence intensity and thermal sensitivity/stability, suitable for an optical temperature sensor/thermal barrier coating. This work aims to develop a fundamental understanding of the local environment surrounding RE or actinide dopants in metal oxide hosts to engineer their luminescence property. To maximize the luminescence, the local symmetry, doping concentration, and radiative/non-radiative relaxation pathways must be …

Characterization Of Gas Hydrate Formation And Its Impact On Slope Stability In Offshore Environments, Sulav Dhakal

LSU Doctoral Dissertations

Natural gas hydrates (NGH) are predominantly methane hydrates formed at high pressure and low temperature conditions typically in submarine sediments and permafrost. This dissertation is focused on the submarine methane hydrates formed by upward migration of free and dissolved gas. The methane gas stored within natural hydrates has more energy potential than all the combined oil and gas resources around the world. Numerical simulation of fluid flow, heat transport, and geomechanical stresses is used to characterize and evaluate the saturation, distribution, reservoir quality, and geohazards associated with hydrate-bearing sediments. Coupled thermo-hydro-mechanical (THM) simulation of hydrate formation, dissociation, and slope stability …

A Drift-Flux Model For Upward Two-Phase In Pipes With High Velocity Flows, Woochan Lee

LSU Doctoral Dissertations

This study proposes the evaluation and development of a drift-flux model for upward two-phase high-velocity flow in large diameter pipes. A case where the proposed model is applicable is WCD (Worst-Case-Discharge) calculations for offshore wells. WCD assumes relatively larger pipe diameters and higher flow rates than the flow experiments at laboratory conditions utilized to validate and develop most of the flow models available in the literature.

Most of the two-phase flow models describe flow regime transitions as discrete processes by assigning the required void fraction or velocity for each flow regime transition. Therefore, for each flow regime, flow-regime-dependent correlations or …

A Data-Based Framework For Monitoring And Controlling Particulate Systems, Vidhyadhar Manee

LSU Doctoral Dissertations

One of the limitations of conventional monitoring tools in crystallization is the inability to deal with high solids concentration. Image-based monitoring, in which RGB images of the solution are captured and analyzed by an object detection software, has been a promising alternative. The software used in these tools primarily depends on hand-coded heuristics to distinguish between the signal and the noise. With the recent success of supervised deep learning, a newer paradigm has emerged in which the heuristics can be learnt from labeled images. This approach is founded on the idea that it is easier to develop labels for data …

Assembly Of Nanostructures At Solid-Liquid And Liquid-Air Interfaces, Yingzhen Ma

LSU Doctoral Dissertations

Molecular and nanoscale colloids such as surfactant, fatty acid and metallic nanoparticles are widely used in numerous applications such as detergents, biomedicine, and catalyst. The assemblies of these colloids show different morphological behavior in aqueous solution due to the wide range of intermolecular interactions such as hydrogen bonding, van der Waals, and electrostatics. The morphology of these assemblies can be changed by environmental factors including temperature, ionic strength, and salinity. However, the guidance to direct assembled state of colloidal assemblies at heterogenous interfaces under various external stimuli remains poorly understand. In this Ph.D. dissertation, we show the adsorption and reconfiguration …

Model-Guided Design Of Rna-Based Synthetic Circuits For The Dynamic Regulation Of Gene Expression, Jordan R. Ryan

LSU Master's Theses

A longstanding goal in synthetic biology has been to build synthetic gene circuits with the ability to harness nature’s capability of precise gene expression regulation. Advancements in RNA technology have established RNA-based regulators with distinct advantages over traditional protein-based regulators such as faster signal propagation, versatile programmability, and low cellular burden, which has created an interest in the field to construct innovative synthetic gene circuits using de novo RNA- based regulators. However, our understanding of the behavior and kinetics of RNA-RNA interactions for the construction of gene circuits is incomplete. This thesis proposes a model-guided design framework that integrates mechanistic …

Visible Light Illuminated Tin Oxide-Gold Nanoparticle Schottky Junctions For H2o2 Generation In Water, Sarah Glass

Honors Capstones

No abstract provided.

Directed 3d Chemotaxis Of Cancer Cells In Response To Oscillating Chemical Gradients Using A Microfluidic Device, Trevor R. Thrasher

Honors Capstones

No abstract provided.

Tuning Electrochemical Interactions And Polymer Electrolyte Interfaces For Enhanced Organic Acid Separations Using Electrodeionization, Matthew Leo Jordan

LSU Doctoral Dissertations

Chemical separations are critical processes for chemical and industrial plants to purify and isolate products however current separation technologies, such as distillation, rely on energy intensive processes. Electrochemical separation processes, such as electrodialysis and electrodeionization, are an energy efficient alternative that are emerging as an alternative for thermal-based separations. Organic acids are weakly ionizable species and susceptible for purification from process streams using electrochemical processes. Recently the fermentation route has garnered greater attention as a means for producing value-added chemicals, such as organic acids, from a renewable feedstock and aiding the circular economy. Some of the challenges electrodialysis faces for …

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, …

Increasing Versatility And Recyclability Of Additive Manufacturing By Utilizing Epdm/Pp Thermoplastic Vulcanizates, Nathan Zeringue

Honors Capstones

No abstract provided.

Heteroaggregation Of Lignin-Zein Nanoparticles: Effects Of Relative Size And Concentration, Yada Chulakham

LSU Master's Theses

Nanotechnology has become an advanced tool for manufacturing materials of the future. As the size of a material is reduced to a nanoscale, its surface area to volume ratio increases drastically, and its surface property becomes size dependent. This allows scientists to make use of unique properties that nanomaterials have to offer to create novel materials that otherwise could not have been achieved in meter-scale materials. As more industrial companies have planned to incorporate different types of nanomaterials into their products, it is undeniable that some of these nanomaterials will be released to the environment. Such possibility has led to …

Application Of Gravity Data For Hydrocarbon Exploration Using Machine Learning Assisted Workflow, Oluwafemi Temidayo Alaofin

LSU Master's Theses

Gravity survey has played an essential role in many geoscience fields ever since it was conducted, especially as an early screening tool for subsurface hydrocarbon exploration. With continued improvement in data processing techniques and gravity survey accuracy, in-depth gravity anomaly studies, such as characterization of Bouguer and isostatic residual anomalies, have the potential to delineate prolific regional structures and hydrocarbon basins. In this study, we focus on developing a cost-effective, quick, and computationally efficient screening tool for hydrocarbon exploration using gravity data employing machine learning techniques. Since land-based gravity surveys are often expensive and difficult to obtain in remote places, …

Cfd Simulations Of Macroscopic And Microscopic Multiphase Fluid Flow And Droplet Interaction, Aaron Harrington

LSU Master's Theses

Multiphase flow is a complex phenomenon which can be modeled on numerous different length scales, both macroscopically and microscopically. The use of a Euler-Euler model for Computation Fluid Dynamics (CFD) simulations of subcooled boiling phenomena is discussed in detail. The CFD conditions have been set up to mimic previous experimental conditions. A cylindrical vessel with subcooled liquid flow is heated along part of the axial wall of the vessel. A constant heat flux is applied to produce subcooled boiling. We discuss the development of the phase change within the vessel as well as the temperature profile, and validate the results …

Reaction Pathways Of Molecular Growth For Bay-Region Methyl-Substituted Polycyclic Aromatic Hydrocarbons During Supercritical Pyrolysis Of N-Decane, Venkata Sai Krishna Karthik Vutukuru

LSU Doctoral Dissertations

Prior to its combustion, fuel for future-highspeed aircraft will experience supercritical conditions, causing the fuel to undergo pyrolytic reactions that lead to the formation of polycyclic aromatic hydrocarbons (PAH), precursors to fuel-line solids that hinder aircraft’s safe operation. Therefore, understanding the formation pathways of PAH under supercritical conditions is important to preventing formation of these solids.

Previous work from our group has shown that n-alkanes are particularly problematic regarding solids formation and that the model fuel n-decane produces an abundance of aliphatics and one- to nine-ring aromatics—many of which are methyl-substituted. Some of these methyl-substituted PAH have their …