Catalysis and Reaction Engineering Commons^™

Enhancements In Mass Transfer For Carbon Capture Solvents Part I: Homogeneous Catalyst, Leland R. Widger, Moushumi Sarma, Jonathan J. Bryant, David S. Mannel, Jesse G. Thompson, Cameron A. Lippert, Kunlei Liu

Center for Applied Energy Research Faculty and Staff Publications

The novel small molecule carbonic anhydrase (CA) mimic [Co^III(Salphen-COO⁻)Cl]HNEt₃ (1), was synthesized as an additive for increasing CO₂ absorption rates in amine-based post-combustion carbon capture processes (CCS), and its efficacy was verified. 1 was designed for use in a kinetically slow but thermally stable blended solvent, containing the primary amines 1-amino-2-propanol (A2P) and 2-amino-2-methyl-1-propanol (AMP). Together, the A2P/AMP solvent and 1 reduce the overall energy penalty associated with CO₂ capture from coal-derived flue gas, relative to the baseline solvent MEA. 1 is also effective at increasing absorption kinetics of kinetically fast solvents, such …

Methanol Steam Reforming: Na Doping Of Pt/Ysz Provides Fine Tuning Of Selectivity, Michela Martinelli, Gary Jacobs, Uschi M. Graham, Burtron H. Davis

Center for Applied Energy Research Faculty and Staff Publications

In this work, we found that sodium doping can be used to improve CO₂ selectivity for supported Pt catalyst during methanol steam reforming. These materials are usually very active in the low temperature range; however, they are characterized by high selectivity of CO, which is a poison in downstream polymer electrolyte membrane fuel cells (PEM-FC) application. With Na doping, we found that CO₂ selectivity was higher than 90% when 2.5 wt.% of sodium was added to Pt/YSZ. We have speculated that the different product distribution is due to a different reaction pathway being opened for CH₃OH …

Tunable Nanocomposite Membranes For Water Remediation And Separations, Sebastián Hernández Sierra

Theses and Dissertations--Chemical and Materials Engineering

Nano-structured material fabrication using functionalized membranes with polyelectrolytes is a promising research field for water pollution, catalytic and mining applications. These responsive polymers react to external stimuli like temperature, pH, radiation, ionic strength or chemical composition. Such nanomaterials provide novel hybrid properties and can also be self-supported in addition to the membranes.

Polyelectrolytes (as hydrogels) have pH responsiveness. The hydrogel moieties gain or lose protons based on the pH, displaying swelling properties. These responsive materials can be exploited to synthesize metal nanoparticles in situ using their functional groups, or to immobilize other polyelectrolytes and biomolecules. Due to their properties, these …

Fractionation And Characterization Of Lignin Streams From Genetically Engineered Switchgrass, Enshi Liu

Theses and Dissertations--Biosystems and Agricultural Engineering

Development of biomass feedstocks with desirable traits for cost-effective conversion is one of the main focus areas in biofuels research. As suggested by techno-economic analyses, the success of a lignocellulose-based biorefinery largely relies on the utilization of lignin to generate value-added products, i.e. fuels and chemicals. The fate of lignin and its structural/compositional changes during pretreatment have received increasing attention; however, the effect of genetic modification on the fractionation, depolymerization and catalytic upgrading of lignin from genetically engineered plants is not well understood. This study aims to fractionate and characterize the lignin streams from a wild-type and two genetically engineered …

Biomimetic Devices To Drive A Thermodynamically Uphill Reaction Using Light And To Degrade Industrial Waste Stream Components, Madison Joanne Sloan

Theses and Dissertations--Chemistry

Given the amount of industrial waste produced each year, as well as the accruing amount of greenhouse gases in our atmosphere produced by the burning of fossil fuels, it is imperative that humanity develop environmentally-sustainable sources of energy and methods of remediation. Nature achieves both of these by use of enzymes as catalysts, inspiring interest in designing biomimetic systems capable of harnessing clean energy and remediating industrial waste. This study examined the ability of enzymes in electrochemical and convective flow systems to achieve these tasks. The first portion studied the incorporation of enzymes into an electrochemical system to drive the …

Synthesis And Energy Applications Of Mesoporous Titania Thin Films, Syed Z. Islam

Theses and Dissertations--Chemical and Materials Engineering

The optical and electronic properties of TiO₂ thin films provide tremendous opportunities in several applications including photocatalysis, photovoltaics and photoconductors for energy production. Despite many attractive features of TiO₂, critical challenges include the innate inability of TiO₂ to absorb visible light and the fast recombination of photoexcited charge carriers. In this study, mesoporous TiO₂ thin films are modified by doping using hydrogen and nitrogen, and sensitization using graphene quantum dot sensitization.

For all of these modifiers, well-ordered mesoporous titania films were synthesized by surfactant templated sol-gel process. Two methods: hydrazine and plasma treatments have been …

Pore-Confined Carriers And Biomolecules In Mesoporous Silica For Biomimetic Separation And Targeting, Shanshan Zhou

Theses and Dissertations--Chemical and Materials Engineering

Selectively permeable biological membranes composed of lipophilic barriers inspire the design of biomimetic carrier-mediated membranes for aqueous solute separation. This work imparts selective permeability to lipid-filled pores of silica thin film composite membranes using carrier molecules that reside in the lipophilic self-assemblies. The lipids confined inside the pores of silica are proven to be a more effective barrier than bilayers formed on the porous surface through vesicle fusion, which is critical for quantifying the function of an immobilized carrier. The ability of a lipophilic carrier embedded in the lipid bilayer to reversibly bind the target solute and transport it through …

Fundamental Studies Of Surfactant Templated Metal Oxide Materials Synthesis And Transformation For Adsorption And Energy Applications, Saikat Das

Theses and Dissertations--Chemical and Materials Engineering

This work addresses fundamental aspects of designing templates and curing conditions for the synthesis of mesoporous metal oxide thin films. The first section addresses selection of cationic-carbohydrate surfactant mixtures to synthesize templated silica thin films for selective adsorption of simple carbohydrates based on molecular imprinting. Nuclear magnetic resonance and fluorescence spectroscopy results suggest a novel structure for mixtures of alkyl glucopyranosides or xylopyranosides with cationic (trimethylammonium) surfactants. Despite thermodynamically favorable mixing, the carbohydrate headgroups in the mixed micelle adopt an inverted configuration with their headgroups in the micelle core, and therefore are inaccessible for molecular imprinting. This orientation occurs even …

Influence Of Reduction Promoters On Stability Of Cobalt/Γ-Alumina Fischer-Tropsch Synthesis Catalysts, Gary Jacobs, Wenping Ma, Burtron H. Davis

Center for Applied Energy Research Faculty and Staff Publications

This focused review article underscores how metal reduction promoters can impact deactivation phenomena associated with cobalt Fischer-Tropsch synthesis catalysts. Promoters can exacerbate sintering if the additional cobalt metal clusters, formed as a result of the promoting effect, are in close proximity at the nanoscale to other cobalt particles on the surface. Recent efforts have shown that when promoters are used to facilitate the reduction of small crystallites with the aim of increasing surface Co⁰ site densities (e.g., in research catalysts), ultra-small crystallites (e.g., < 2–4.4 nm) formed are more susceptible to oxidation at high conversion relative to larger ones. The choice of promoter is important, as certain metals (e.g., Au) that promote cobalt oxide reduction can separate from cobalt during oxidation-reduction (regeneration) cycles. Finally, some elements have been identified to promote reduction but either poison the surface of Co⁰ (e.g., Cu), or produce excessive light gas selectivity (e.g., Cu and Pd, or Au at …

Mixed Surfactant Systems: Thermodynamics And Applications In Metal Oxide Imprinting, Suvid Joshi

Theses and Dissertations--Chemical and Materials Engineering

In this work we study mixtures of cationic surfactant (CTAB) and sugar based surfactant(s) (octyl beta-D-glucopyranoside (C8G1), dodecyl maltoside (C12G2) and octyl beta-D-xylopyranoside (C8X1)) to understand the non-ideal thermodynamic behavior of the mixtures of cationic and non-ionic surfactants in water and synthesis of imprinted materials. The thermodynamics of micellization, mixing and dilution of these systems are studied using Isothermal Titration Calorimetry (ITC) and the experimental data obtained are modeled with a pseudo-phase separation model with non-ideal mixing described by regular solution theory. It is shown that a model accounting for enthalpy of demicellization and enthalpy of dilution based on McMillan-Mayer …

Effects Of Sodium Hydroxide Pretreatment On Structural Components Of Biomass, Alicia A. Modenbach, Sue E. Nokes

Biosystems and Agricultural Engineering Faculty Publications

Pretreatment is a unit operation in the conversion of biomass to valuable products that utilizes various combinations of conditions, including chemicals, heat, pressure, and time, to reduce the recalcitrance of lignocellulose. Many such pretreatments have been developed over the years, as the operating conditions can be adapted so that lignocellulose is modified in ways unique to each pretreatment. By tailoring pretreatment conditions to achieve these modifications, the types of final products produced can be controlled. The purpose of this review is to provide a consolidated source of information for sodium hydroxide effects on lignocellulose. The structural characteristics of lignocellulose and …

Quartz Crystal Microbalance Investigation Of Cellulosome Activity From Clostridium Thermocellum On Model Cellulose Films, Shanshan Zhou

Theses and Dissertations--Chemical and Materials Engineering

The cost of deconstructing cellulose into soluble sugars is a key impediment to the commercial production of lignocellulosic biofuels. The use of the quartz crystal microbalance (QCM) to investigate reaction variables critical to enzymatic cellulose hydrolysis is investigated here, extending previous studies of fungal cellulase activity for the first time to whole cell cellulases. Specifically, the activity of the cellulases of Clostridium thermocellum, which are in the form of cellulosomes, was investigated. To clearly differentiate the activity of free cellulosome and cell-bound cellulosome, the distribution of free cellulosome and cell-bound cellulosome in crude cell broth at different growth stages …

Functionalized Membranes For Environmental Remediation And Selective Separation, Li Xiao

Theses and Dissertations--Chemical and Materials Engineering

Membrane process including microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) have provided numerous successful applications ranging from drinking water purification, wastewater treatment, to material recovery. The addition of functional moiety in the membranes pores allows such membranes to be used in challenging areas including tunable separations, toxic metal capture, and catalysis. In this work, polyvinylidene fluoride (PVDF) MF membrane was functionalized with temperature responsive (poly(N-isopropylacrylamide), PNIPAAm) and pH responsive (polyacrylic acid, PAA) polymers. It’s revealed that the permeation of various molecules (water, salt and dextran) through the membrane can be thermally or pH controlled. The introduction of …

Layer-By-Layer Assemblies For Membrane-Based Enzymatic Catalysis, Andrew R. Tomaino

Theses and Dissertations--Chemical and Materials Engineering

While considerable progress has been made towards understanding the effect that membrane-based layer-by-layer (LbL) immobilizations have on the activity and stability of enzymatic catalysis, detailed work is required in order to fundamentally quantify and optimize the functionalization and operating conditions that define these properties. This work aims to probe deeper into the nature of transport mechanisms by use of pressure-induced, flow-driven enzymatic catalysis of LbL-functionalized hydrophilized poly(vinyldiene) (PVDF)-poly(acrylic acid) (PAA)-poly(allylamine hydrochloride) (PAH)-glucose oxidase (GOx) membranes. These membranes were coupled in a sealed series following cellulose acetate (CA) membranes for the elimination of product accumulation within the feed-side solution during operation. …

The Effects Of Ceria Addition On Aging And Sulfation Of Lean Nox Traps For Stand Alone And Lnt-Scr Applications, Vencon G. Easterling

Theses and Dissertations--Chemical and Materials Engineering

THE EFFECTS OF CERIA ADDITION ON AGING AND SULFATION OF LEAN NO_x TRAPS FOR STAND ALONE AND LNT-SCR APPLICATIONS

Model powder and fully formulated monolithic lean NO_x trap (LNT) catalysts were used to investigate the effect of ceria on desulfation behavior. Temperature-programmed reduction (TPR) experiments (model catalysts) showed each of the oxide phases present is able to store sulfur and possesses distinct behavior (temperature at which desulfation occurs). La-CeO₂ or CeO₂-ZrO₂-containing samples (monoliths) showed a greater resistance to deactivation during sulfation and required lower temperatures to restore the NO_x storage efficiency to …

Application Of Thin Film Analysis Techniques And Controlled Reaction Environments To Model And Enhance Biomass Utilization By Cellulolytic Bacteria, Hsin-Fen Li

Theses and Dissertations--Chemical and Materials Engineering

Cellulose from energy crops or agriculture residues can be utilized as a sustainable energy resource to produce biofuels such as ethanol. The process of converting cellulose into solvents and biofuels requires the saccharification of cellulose into soluble, fermentable sugars. However, challenges to cellulosic biofuel production include increasing the activity of cellulose-degrading enzymes (cellulases) and increasing solvent (ethanol) yield while minimizing the co-production of organic acids. This work applies novel surface analysis techniques and fermentation reactor perturbations to quantify, manipulate, and model enzymatic and metabolic processes critical to the efficient production of cellulosic biofuels.

Surface analysis techniques utilizing cellulose thin film …

Effects Of Growth Media Ph And Reaction Water Activity On The Conversion Of Acetophenone To (S)-1-Phenylethanol By Saccharomyces Cerevisiae Immobilized On Celite 635 And In Calcium Alginate, Nicholas P. Coleman, Czarena Crofcheck, Sue E. Nokes, Barbara L. Knutson

Biosystems and Agricultural Engineering Faculty Publications

Biologically catalyzed reactions often produce enantiomers of the product; however, only one configuration is desired. Reaction conditions are known to affect enantiomer ratios and reaction kinetics, but little is known regarding the effect of processing conditions on whole-cell biocatalysis. Saccharomyces cerevisiae cells were grown in batch on glucose at pH = 4, 5, and 7, and then immobilized on Celite beads or in calcium alginate beads and used as the biocatalyst for the conversion of acetophenone in hexane to (S)-1-phenylethanol at water activities of 0.37, 0.61, and 0.80. S. cerevisiae was used as a model microorganism for the whole-cell catalyzed …