Chemical Engineering Commons^™

Revisiting The Volumetric Swing Frequency Response Method For The Determination Of Limiting Mass Transfer Mechanisms Of N2 And O2 In Carbon Molecular Sieve 3k172, Adam Marshall Burke

Theses and Dissertations

Adsorption-based separations processes, along with the adsorbents that enable them, have benefited from a greater particular focus in recent years, following a desire to improve process energy efficiencies and cost economics. One such adsorbent, carbon molecular sieves (CMS), have likewise been a greater focus. CMS materials offer several key practical uses, such as the separation of nitrogen and oxygen, and the removal of carbon dioxide from methane process streams. In order to effectively design and implement an industrial scale process using a CMS material, the behavior of these gases on the chosen material must be known, including the limiting mass …

New Perspectives And Insights Into Direct Epoxidation Of C3H6 Using O2 And Ag Based Catalysts And Measurement Of Active Ag Site Concentration Of Promoted Ag Catalyst For C2H4 Epoxidation By H2 Pulse Titration Over Oxygen Pre-Covered Surface, Md Masudur Rahman

Theses and Dissertations

Direct epoxidation of C₃H₆ using molecular O₂ and Ag catalysts to produce propylene oxide (PO) selectively is a long-sought goal in the field of heterogeneous catalysis. In the early 1990’s Scientists at ARCO reported promising results of 58 – 59% selectivity to PO at 3.2% conversion of C₃H₆ over an unusual composition of 54.0 wt% Ag, 2.0 wt% K⁺, 0.5 wt% Mo and balance CaCO₃. Feed additives of ethyl chloride (EtCl), nitric oxide (NO) and CO₂ were stated necessary to achieve the claimed high PO selectivities. The roles …

Mathematical Analysis Of Electrochemical Systems, Shiv Krishna Reddy Madi Reddy

Theses and Dissertations

A solid electrolyte interphase (SEI) growth model is developed in a mixed modethat contains solvent diffusion through the SEI layer and corresponding solvent reduction kinetics at the SEI/electrode interface. The governing equations are solved by the Landau transformation, which makes the moving layer fixed to predict the open circuit potential, SEI layer thickness, and capacity loss. The estimated parameters fitted with experimental data from the literature are computed using COMSOL and MATLAB. Results show that the mixed mode model predicts lower capacity loss and thinner SEI layer due to its growth under open circuit conditions than previously reported by others. …

Durability Enhancement Of Anion Exchange Membrane Based Fuel Cells (Aemfcs) And Water Electrolyzers (Aemels) By Understanding Degradation Mechanisms, Noor Ui Hassan

Theses and Dissertations

The past several years have seen remarkable progress in renewable energy sources such as solar and wind, showing excellent efficiency and significant cost reduction. The intermittent nature of renewable resources requires them to be integrated with energy storage systems that can hold or convert this excess energy into other forms. Though batteries have been the most popular, it is also possible to store the energy as chemicals and fuels, such as hydrogen (H₂). Hydrogen generation from water electrolysis has been receiving significant attention in recent years. Among the existing water electrolysis technologies, anion exchange membrane electrolyzers (AEMELs) are …

Supported Metal Bifunctional And Bimetallic Catalysts With Precisely Controlled Structures And Properties, Anhua Dong

Theses and Dissertations

In heterogenous catalysis, metallic nanomaterials play vital roles in numerous chemical processes. However, monofunctional catalysts are greatly impeded in their applications especially in the systems including tandem and/or sequential reaction steps. Besides, the catalytic performance can also be greatly influenced by the particle size, morphology, and geometry of the surface metal atoms.

The goal of this work is to synthesize bifunctional or bimetallic nanoparticles with high metal dispersion and homogenous alloys by rational synthetic strategies to facilitate the catalyst function. Strong electrostatic adsorption (SEA) is an effective and facile methodology to produce well dispersed and uniform nanoparticles. Metal-acid bifunctional catalysts …

Molecular Theoretical Model For Lipid Bilayers: Adsorption Of Lipidated Proteins On Lipid Bilayers As A Function Of Bilayer Composition And Curvature, Shauna Celeste Kennard

Theses and Dissertations

Protein localization on biological membranes is motivated by either highly selective recognition of specific target membrane components or nonspecific attraction to general physical properties of the membrane, such as charge, lipid heterogeneity, and curvature. Here we discuss the interaction between lipidated proteins and lipid bilayer membranes from a comprehensive examination of how features of the membrane and its lipid constituents, including lipid composition, headgroup size, degree of tail saturation, tail length (bilayer thickness), and membrane geometry, affect the adsorption ability of the proteins. Of key importance is the strong interconnection among these compositional and morphological elements of the membrane in …

Chiral Liquid Crystal Microdroplets For Sensing Phospholipid Amphiphiles, Sepideh Norouzi, Jose A. Martinez Gonzalez, Monirosadat (Sanaz) Sadati

Faculty Publications

Designing simple, sensitive, fast, and inexpensive readout devices to detect biological molecules and biomarkers is crucial for early diagnosis and treatments. Here, we have studied the interaction of the chiral liquid crystal (CLC) and biomolecules at the liquid crystal (LC)-droplet interface. CLC droplets with high and low chirality were prepared using a microfluidic device. We explored the reconfiguration of the CLC molecules confined in droplets in the presence of 1,2-diauroyl-sn-glycero3-phosphatidylcholine (DLPC) phospholipid. Cross-polarized optical microscopy and spectrometry techniques were employed to monitor the effect of droplet size and DLPC concentration on the structural reorganization of the CLC molecules. Our results …

Chiral Liquid Crystal Microdroplets For Sensing Phospholipid Amphiphiles, Sepideh Norouzi, Jose A. Martinez Gonzalez, Monirosadat Sadati

Faculty Publications

Designing simple, sensitive, fast, and inexpensive readout devices to detect biological molecules and biomarkers is crucial for early diagnosis and treatments. Here, we have studied the interaction of the chiral liquid crystal (CLC) and biomolecules at the liquid crystal (LC)-droplet interface. CLC droplets with high and low chirality were prepared using a microfluidic device. We explored the reconfiguration of the CLC molecules confined in droplets in the presence of 1,2-diauroyl-sn-glycero3-phosphatidylcholine (DLPC) phospholipid. Cross-polarized optical microscopy and spectrometry techniques were employed to monitor the effect of droplet size and DLPC concentration on the structural reorganization of the CLC molecules. Our results …

Editorial For Gels 6th Anniversary Special Issue, Esmaiel Jabbari, Gulden Camci-Unal

Faculty Publications

Note: In lieu of an abstract, this is an excerpt from the first page.

This Special Issue celebrates many outstanding quality papers published in Gels over the past six years since its first issue was published in 2015 [...]

Antiviral Polymers: A Review, Ali Akbari, Ashkan Bigham, Vahid Rahimkhoei, Sina Sharifi, Esmaiel Jabbari

Faculty Publications

Polymers, due to their high molecular weight, tunable architecture, functionality, and buffering effect for endosomal escape, possess unique properties as a carrier or prophylactic agent in preventing pandemic outbreak of new viruses. Polymers are used as a carrier to reduce the minimum required dose, bioavailability, and therapeutic effectiveness of antiviral agents. Polymers are also used as multifunctional nanomaterials to, directly or indirectly, inhibit viral infections. Multifunctional polymers can interact directly with envelope glycoproteins on the viral surface to block fusion and entry of the virus in the host cell. Polymers can indirectly mobilize the immune system by activating macrophages and …

Editorial For Gels 6th Anniversary Special Issue, Esmaiel Jabbari, Gulden Camci-Unal

Faculty Publications

No abstract provided.

Observing And Modeling Water Electrolysis Performance Limitations Attributed To Gas Generation And Porous Media Properties, Joseph S. Lopata

Theses and Dissertations

Water electrolysis has been a simple method of hydrogen production for over two centuries, but the exploration of its nuances is still accelerating. This work compiles numerous mechanisms via which electrolysis efficiency is influenced by phenomena that occur within, adjacent to, and nearby functional porous media. Computational and experimental methods are applied to electrolysis systems to quantify the impact of twophase flow patterns and porous media properties on energy losses, primarily those linked directly to the presence of the gas phase.

First, an introduction to the chemistry and operating principle of water electrolysis is presented and relevant works from the …

Synthesis, Characterization And Evaluation Of Dilute Limit Alloy Bimetallic Catalysts For Bio-Oil Upgrading, Leandro Tagum De Castro

Theses and Dissertations

Well-defined single-atom catalytic sites with unique geometric and electronic properties are at the forefront of catalyst research. One type of SAC is a so-called dilute limit alloy (DLA), where single metal atom sites are supported on (or in) the surface of a second metal. This category of well-dispersed atoms alloyed on a metal surface has shown to be effective in reactions like selective hydrogenation of alkynes and dienes to alkenes, ethanol dehydrogenation, and the Ullmann reaction of aryl chlorides. In biomass conversion, this type of catalyst may find its way to address and improve conversion and yield that are crucial …

Highly Active And Stable Low-Pgm And Pgm-Free Catalysts For Anion Exchange Membrane Fuel Cells, Horie Adabi Firouzjaie

Theses and Dissertations

Anion exchange membrane fuel cells (AEMFCs) have recently seen significant growth in interest as their achievable current density, peak power density, and longevity have been dramatically improved. Though these advances in performance have been important for demonstrating the feasibility of the technology, nearly all AEMFCs reported in the literature have required a relatively high loading of platinum group metal (PGM)- based catalysts at both the anode and cathode electrodes. However, to take command of the low-temperature fuel cell market, AEMFCs cannot simply reach the same performance as incumbent proton exchange membrane fuel cells (PEMFCs), which have had decades of development …

Catalytic Cracking Of Oxygenated Polymer Waste Via Zeolite Catalysts, Andrew Jaeschke

Theses and Dissertations

Plastic recycling has been a prevalent issue since the commercialization of plastics due to lack of adoption and insufficient technology. There are many different types of plastics used in modern day society; however, majority of recycling efforts are focused solely on polyethylene terephthalate (PET) and polyethylene plastics. Some of these overlooked plastics include polyols and polyurethanes, which can be found in a variety of applications including furniture stuffing, adhesives, and insulation foams. Recently, plastic research has turned to catalytic cracking units as a means of plastic recyclability. Catalytic cracking of hydrocarbons is a field dominated by zeolites catalysts, especially ZSM-5. …

Rational Synthesis Of Ultra-Small And Durable Platinum-Based Catalysts For Renewable Energy Applications, Fahim Bin Abdur Rahman

Theses and Dissertations

Ultrasmall supported platinum nanoparticles (Pt NPs) are often used in two promising renewable energy production technologies – hybrid-sulfur water splitting for actively catalyzing H2SO4 decomposition and in fuel cells for the oxygen reduction reaction (ORR). However, the stability of Pt NPs under reaction conditions is the ultimate challenge for these processes. Two prevalent ways to overcome this challenge are improving stability by anchoring Pt onto a secondary metal or doping heteroatoms into the support. This dissertation covers the rational design, synthesis, and stabilization of Pt-based catalysts in these two ways to achieve durable catalytic performance with desired activity and selectivity. …

Decellularized Articular Cartilage Microgels As Microcarriers For Expansion Of Mesenchymal Stem Cells, Esmaiel Jabbari, Azadeh Sepahvandi

Faculty Publications

Conventional microcarriers used for expansion of human mesenchymal stem cells (hMSCs) require detachment and separation of the cells from the carrier prior to use in clinical applications for regeneration of articular cartilage, and the carrier can cause undesirable phenotypic changes in the expanded cells. This work describes a novel approach to expand hMSCs on biomimetic carriers based on adult or fetal decellularized bovine articular cartilage that supports tissue regeneration without the need to detach the expanded cells from the carrier. In this approach, the fetal or adult bovine articular cartilage was minced, decellularized, freeze-dried, ground, and sieved to produce articular …

Hydrodeoxygenation Of Biomass Derived Sugar Alcohols To Platform Chemicals Using Heterogeneous Catalysts, Blake Macqueen

Theses and Dissertations

This work set out to investigate biomass derived sugar alcohol upgrading via the removal of oxygen and hydroxyl groups via the hydrodeoxygenation reaction utilizing heterogeneous catalysts. The importance of reaction conditions, catalyst meal loadings, catalyst structure and properties were probed using techniques such as design of experiments, and spectroscopic techniques including Raman and DRIFTS. The state of the art simultaneous hydrodeoxygenation (S-HDO) catalyst ReO_x-Pd/CeO₂ was investigated and optimized for various sugar alcohol substrates. The kinetics and associated mass transfer were also investigated to give further insight into the reaction over the ReO_xPd/CeO₂ catalyst.

First, …

Fine Points For Broad Bumps: The Extension Of Rietveld Refinement For Benchtop Powder Xrd Analysis Of Ultra-Small Supported Nanoparticles, Jeremiah W. Lipp

Theses and Dissertations

The goal of this work is to demonstrate the capabilities of benchtop Bragg diffraction in characterizing ultra-small (< 2nm) nanoparticles. To this end we have established a method for accurately separating the background, adjusting for relevant intensity effects, and analyzing the results with Rietveld refinement. This method is applied to the characterization of six silica-supported “noble” metals under ambient conditions: Pt, Pd, Ir, Rh, Ru, and Au. Surprisingly, Bragg diffraction is capable of shining light on this difficult-to-characterize size region – revealing the propensity of these metal nanoparticles to oxidize at room temperature. Preliminary findings for future work are also discussed: extending our method to crystalline supports and fluorescent samples.

Preparation, Characterization And Evaluation Of Rationally Designed Catalysts By Electroless Deposition, Wen Xiong

Theses and Dissertations

In heterogeneous catalysis, it is a proven factor that the surface-specific activity and the catalyst selectivity strongly depends on the active sites which are determined by the composition, size, and shape of the particle. For structure-sensitive reactions favored by specific surface sites, such as corners, steps, or edges, TOF and selectivity can be greatly changed by the size of catalyst particles since the active site distribution will change with the size of the catalysts. Usually, metal particles are synthesized by two methods in industry, namely precipitation and impregnation, which often exhibit a broad size distribution. The grand challenge of colloidal …

Quantifying And Elucidating The Effect Of Co2 On Aemfcs, Yiwei Zheng

Theses and Dissertations

Anion exchange membrane fuel cells (AEMFCs) have recently received significant attention as a future high efficiency, environmentally friendly energy conversion device. This attention is due to the potential advantages that AEMFCs can offer compared the much more common, and commercialized, proton exchange membrane fuel cells (PEMFCs) – most notably lower cost. However, there are several remaining roadblocks for the AEMFC technology to be widely adopted, such as: i) the stability of the anion exchange membranes (AEMs) and anion exchange ionomer (AEIs); ii) the development of highly active catalysts with either low platinum group metal (PGM) loading or catalysts that are …

Structure And Stability Of Ag-Ir Bimetallic Catalysts Prepared By Electroless Deposition And Synthesis And Performance Of High Selectivity Movnbsbteox Mixed Oxides For Oxidative Dehydrogenation Of Ethane, Mozhdeh Parizad

Theses and Dissertations

Improvements in industrial thermal conversions can be realized through comprehensive catalytic studies, where enhanced catalyst stability and activity are desired. Catalyst performance can be greatly affected by structural changes at high temperatures. In the case of supported Ag-Ir particles, the surface free energy (SFE) can determine preferred arrangement of the component metals. The well-established methods of strong electrostatic adsorption (SEA) and electroless deposition (ED) have been used to synthesize highly-dispersed Ag/Ir on different alumina supports (δ,θ-Al2O3 and γ-Al2O3). Surface thermodynamics dictate that the Ir-Ag system should conform to minimize free energy resulting in a low SFE Ag layer localized on …

Recent Advances In Catalytic Ethylene Epoxidation: Synthesis, Characterization, And Evaluation, Benjamin Thomas Egelske

Theses and Dissertations

First synthesized in 1859 by French chemist Charles-Adolphe Wurtz, ethylene oxide (EO) is produced from the direct epoxidation of ethylene and molecular oxygen over a low surface area α-Al₂O₃ supported silver (Ag) catalyst [1-6]. With a production capacity over 35 Mt/year, EO is the largest chemical by volume synthesized from a heterogeneously catalyzed process and is used in the production of ethylene glycol, ethoxylates, and ethanolamines [6, 7]. State-of-the-art catalyst formulations contain high loadings of Ag, typically 12-30wt%, required to recover activity in the presence of promoter elements which increase EO selectivity from ~75% for unsupported Ag to 80% for …

Development Of A Multi-Scale Mechano-Electrochemical Battery Model, Drew J. Pereira

Theses and Dissertations

As the automotive industry moves towards large format electric vehicles, such as trucks and SUVs, the need for highly efficient, energy-dense electrodes rapidly increases. Several promising active materials have been studied and proposed, however, many of these materials undergo significant volume change upon lithiation and de-lithiation. Cell and pack designers struggle to understand and predict how active material volume change at the particle scale will affect mechano-electrochemical behavior on the electrode, cell, and pack scales. Additionally, many of these active materials suffer in their cycle life due to a mechanically-driven degradation of the electrode matrix. Therefore, the focus of this …

Catalytic And Non-Catalytic Methods For Hydrocarbon Upgrading, Valorization, And Pollutant Control, Michael Morgan Royko

Theses and Dissertations

This work investigates catalytic and non-catalytic oxidative chemical upgrading and pollutant remediation techniques to responsibly utilize hydrocarbon feedstocks with existing infrastructure as the transition to more renewable and cleaner feedstocks for energy generation are developed. These technologies include oxidative dehydrogenation of ethane, development of magnetically separable catalysts to reduce carbon monoxide emissions during biomass upgrading as well as the subsequent use of the upgraded biomass for partial coal replacement, and electrochemical treatment of a washcoat free wire mesh supported catalyst to reduce carbon monoxide emissions in combustion exhaust.

First, doping of secondary metals in M1/M2 catalysts for oxidative dehydrogenation of …

Insights Into Rational Catalysts Synthesis, Abolfazl Shakouri

Theses and Dissertations

Atomically distributed metal centers with maximized atom utilization efficiency called single-atom catalysts (SACs) have attracted significant attention in catalysis. SACs with the advantages of both homogeneous and heterogeneous catalysts have been rising as a new frontier in the field of catalysis. New catalytic technologies are ever-growing, considering 90% of all chemical processes employ catalysts, securing modern society’s sustainable future. A classical field in catalysis has been dedicated to catalysis by supported metals. Recently, a vast effort has been devoted to smaller catalyst particles where size is restricted to a single atom on a surface. Single atoms supported or embedded on …

Mathematical Model For Sei Growth Under Open-Circuit Conditions, Wei Shang

Theses and Dissertations

An irreversible capacity loss will take place in lithium ions batteries due to the solid electrolyte interface (SEI) creating, which consumes the active lithium and reduces solvent. SEI is either good since it can prevent further electrolyte decomposition or bad for lessening batteries' lifetime. Mathematical modeling of SEI formation is done within a porous electrode to model an empirical battery in the x-direction.A solid electrolyte interphase (SEI) growth model is developed in a mixed-mode which contains solvent diffusion through the SEI layer and its corresponding kinetics of solvent reduction at the electrode surface. The governing equations are numerically solved by …

Shape-Selective Silver Catalysts For Ethylene Epoxidation, Kaveh Shariati

Theses and Dissertations

Epoxidation of ethylene with oxygen over promoted silver catalyst is one of the most important examples of heterogeneous catalysis to date with a multi-billion dollar annual market. Ethylene oxide (EO) can be used directly as a sterilizer, disinfectant, and fungicide, or as an intermediate chemical for producing ethylene glycol, detergents, antifreeze, polyesters, as well as a variety of other commercial chemicals. Thus, ethylene oxide is known as one of the highest volume chemicals produced in the chemical industry, accounting for approximately 40-50% of the total value of organic chemicals produced by heterogeneous oxidation. Considering the application of EO in detergents …

The Effects Of Ceria Loading On Three-Way Catalysts For Passive Scr Operation, Calvin R. Thomas, Josh A. Pihl, Vitaly Y. Prikhodko, Michelle K. Kidder, Jochen A. Lauterbach, Todd J. Toops

Faculty Publications

Passive SCR systems, which employ both a three-way catalyst and SCR catalyst, are effective for the reduction of nitrogen oxide (NOx) emissions from lean burn gasoline engines. However, questions remain regarding the effect of three-way catalyst formulations on their performance in these systems. Here, Pd/CeOx/Al2O3 catalysts with variable CeOx loading were synthesized, characterized, and evaluated to determine the effects of CeOx on catalyst performance. While a small amount of ceria was beneficial for promoting essential reactions, excess ceria was detrimental due to the increase in oxygen storage capacity. Additionally, insights into potential reaction pathways for NH3 production were determined.

The Effects Of Ceria Loading On Three-Way Catalysts For Passive Scr Operation, Calvin R. Thomas, Josh A. Pihl, Vitaly Y. Prikhodko, Michelle K. Kidder, Jochen A. Lauterbach, Todd J. Toops

Faculty Publications

Passive SCR systems, which employ both a three-way catalyst and SCR catalyst, are effective for the reduction of nitrogen oxide (NOx) emissions from lean burn gasoline engines. However, questions remain regarding the effect of three-way catalyst formulations on their performance in these systems. Here, Pd/CeOx/Al2O3 catalysts with variable CeOx loading were synthesized, characterized, and evaluated to determine the effects of CeOx on catalyst performance. While a small amount of ceria was beneficial for promoting essential reactions, excess ceria was detrimental due to the increase in oxygen storage capacity. Additionally, insights into potential reaction pathways for NH3 production were determined.