Chemical Engineering Commons^™

Atomic Layer Deposition Prepared Nanostructured Materials For Various Catalytic Reactions, Xiaofeng Wang

Doctoral Dissertations

"Atomic layer deposition (ALD) has been widely used for thin film coating and metal nanoparticles (NPs) preparation. In this report, the applications of ALD prepared nanostructured materials in catalysis were examined.

Highly dispersed Pt monometallic catalysts with different substrates and multi-walled carbon nanotubes (MWCNTs) supported Pt-Co bimetallic catalysts were synthesized by ALD for selective hydrogenation of α, β-unsaturated aldehydes to unsaturated alcohols (UA). Pt/MWCNTs showed the highest selectivity of UA in selective hydrogenation of citral, as compared to Pt/SiO₂, Pt/ALD-Al₂O₃, and Pt/γ-Al₂O₃. After adding Co, the highest selectivity was achieved …

Synergistic Interactions Of H2 And N2 With Molten Gallium In The Presence Of Plasma, Maria L. Carreon, Daniel F. Jaramillo-Cabanzo, Indira Chaudhuri, Madhu Menon, Mahendra K. Sunkara

Physics and Astronomy Faculty Publications

The present study examines the interaction of hydrogen and nitrogen plasmas with gallium in an effort to gain insights into the mechanisms behind the synergetic effect of plasma and a catalytic metal. Absorption/desorption experiments were performed, accompanied by theoretical-computational calculations. Experiments were carried out in a plasma-enhanced, Ga-packed, batch reactor and entailed monitoring the change in pressure at different temperatures. The results indicated a rapid adsorption/dissolution of the gas into the molten metal when gallium was exposed to plasma, even at a low temperature of 100 °C. The experimental observations, when hydrogen was used, indicate that gallium acts as a …

Copper Oxide Nanoparticles As A Highly Efficient Catalyst For Catalysis Applications, Hany A. Elazab Dr

Chemical Engineering

In this research, we have developed a reliable green method for the synthesis of copper oxide nanoparticles as a potential efficient catalyst for several catalysis applications. In our experimental approach, microwave-assisted synthesis technique was used in order to perform chemical reduction of copper salt using hydrazine hydrate as a strong reducing agent. The prepared catalyst was characterized using various techniques showing the formation of well dispersed copper oxide nanoparticles. The synthesized Copper oxide catalyst shows many advantages including the use of environmentally benign solvent systems, green synthetic approach, and mild reaction conditions.

The Effect Of Graphene On Catalytic Performance Of Palladium Nanoparticles Decorated With Fe3o4, Co3o4, And Ni (Oh)2: Potential Efficient Catalysts Used For Suzuki Cross—Coupling, Hany A. Elazab, Sherif Moussa, Ali R. Siamaki, B. Frank Gupton, M. Samy El-Shall

Chemical and Biochemical Engineering Faculty Research & Creative Works

Abstract: In this research, we report a scientific investigation of an efficient method used for the synthesis of highly active Palladium Nanoparticles decorated with Fe₃O₄, Co₃O₄, and Ni (OH)2 Supported on Graphene as Potential Efficient Catalysts for Suzuki Cross—Coupling. Pd/Fe₃O₄ nanoparticles supported on graphene nanosheets (Pd/Fe₃O₄/G) showed an excellent catalytic activity for Suzuki coupling reactions and recycled for up to four times without loss of catalytic activity. An efficient magnetic catalyst has been successfully synthesized using a simple, reproducible fast and reliable method using microwave …

Pore Functionalized Pvdf Membranes With In-Situ Synthesized Metal Nanoparticles: Material Characterization, And Toxic Organic Degradation, Hongyi Wan, Nicolas J. Briot, Anthony Saad, Lindell E. Ormsbee, Dibakar Bhattacharyya

Chemical and Materials Engineering Faculty Publications

Functionalized PVDF membrane platforms were developed for environmentally benign in-situ nanostructured Fe/Pd synthesis and remediation of chlorinated organic compounds. To prevent leaching and aggregation, nanoparticle catalysts were integrated into membrane domains functionalized with poly (acrylic acid). Nanoparticles of 16–19 nm were observed inside the membrane pores by using focused ion beam (FIB). This technique prevents mechanical deformation of the membrane, compared to the normal SEM preparation methods, thus providing a clean, smooth surface for nanoparticles characterization. This allowed quantification of nanoparticle properties (size and distribution) versus depth underneath the membrane surface (0–20 μm). The results showed that nanoparticles were uniformly …

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 …

Synthesis And Catalytic Applications Of Non-Metal Doped Mesoporous Titania, Syed Z. Islam, Suraj R. Nagpure, Doo Young Kim, Stephen E. Rankin

Chemical and Materials Engineering Faculty Publications

Mesoporous titania (mp-TiO₂) has drawn tremendous attention for a diverse set of applications due to its high surface area, interfacial structure, and tunable combination of pore size, pore orientation, wall thickness, and pore connectivity. Its pore structure facilitates rapid diffusion of reactants and charge carriers to the photocatalytically active interface of TiO₂. However, because the large band gap of TiO₂ limits its ability to utilize visible light, non-metal doping has been extensively studied to tune the energy levels of TiO₂. While first-principles calculations support the efficacy of this approach, it is challenging to …

The Effect Of Graphene On Catalytic Performance Of Palladium Nanoparticles Decorated With Fe3o4, Co3o4, And Ni (Oh)2: Potential Efficient Catalysts Used For Suzuki Cross—Coupling, Hany A. Elazab Dr

Chemical Engineering

In this research, we report a scientific investigation of an efficient method used for the synthesis of highly active Palladium Nanoparticles decorated with Fe3O4, Co3O4, and Ni (OH)2 Supported on Graphene as Potential Efficient Catalysts for Suzuki Cross—Coupling. Pd/Fe3O4 nanoparticles supported on graphene nanosheets (Pd/ Fe3O4/G) showed an excellent catalytic activity for Suzuki coupling reactions and recycled for up to four times without loss of catalytic activity. An efficient magnetic catalyst has been successfully synthesized using a simple, reproducible fast and reliable method using microwave irradiation conditions. The prepared catalysts are magnetic as in case of iron and cobalt oxides …

Fundamental Investigation Of The Electrocatalytic Activity Of Layered Mixed Metal Oxides For Low Temperature Oxygen Electrocatalysis, Ayad M. Nacy

Wayne State University Dissertations

Li–O2 (Li–air) batteries are among the most promising energy storage technologies due to their high theoretical specific capacity and energy density. Key challenges with this technology include high overpotential losses associated with catalyzing the electrochemical reactions (i.e., oxygen reduction and evolution reactions) at the cathode of the battery. One way to address this challenge is to incorporate an active electrocatalyst, such as first-order Ruddlesden-Popper series of layered oxides. We show that the composition of the A-site in first-order Ruddlesden-Popper series of layered oxides (A2BO4) has a significant effect in the electrochemical activity of Li-O2 cathodes. Among the oxides composed of …

Catalytic Hydrotreatment For The Development Of Renewable Transportation Fuels, Lilu Funkenbusch

Dissertations, Master's Theses and Master's Reports

Biologically-derived feedstocks are a highly desirable source of renewable transportation fuel. They can be grown renewably and can produce fuels similar in composition to conventional fossil fuels. They are also versatile and wide-ranging. Plant oils can produce renewable diesel and wood-based pyrolysis oils can be made into renewable gasoline. Catalytic hydrotreatment can be used to reduce the oxygen content of the oils and increase their viability as a “drop-in” transportation fuel, since they can then easily be blended with existing petroleum-based fuels. However, product distribution depends strongly on feedstock composition and processing parameters, especially temperature and type of catalyst. Current …

Green Synthesis Of Copper Oxide Nanoparticles In Aqueous Medium As A Potential Efficient Catalyst For Catalysis Applications, Waad Mohsen, M. A. Sadek, Hany A. Elazab

Chemical and Biochemical Engineering Faculty Research & Creative Works

In this research, we have developed a reliable green method for the synthesis of copper oxide nanoparticles as a potential efficient catalyst for several catalysis applications. In our experimental approach, microwave-assisted synthesis technique was used in order to perform chemical reduction of copper salt using hydrazine hydrate as a strong reducing agent. The prepared catalyst was characterized using various techniques showing the formation of well dispersed copper oxide nanoparticles. The synthesized Copper oxide catalyst shows many advantages including the use of environmentally benign solvent systems, green synthetic approach, and mild reaction conditions.

Production Of Glycerol 1,2-Carbonate From Glycerol With Aid Of Ionic Liquid As Catalyst, Nor Asrina Sairi, Zati Ismah, Yatimah Alias, Rozita Yusoff, Mohamed Kheireddine Taieb Aroua,

5th International Congress on Green Process Engineering (GPE 2016)

The surplus formation of glycerol (glycerine or 1,2,3-propanetriol) during biodiesel production has led to a major concern. Glycerol price has dropped and it exerts a great impact on the refined glycerol market. This has triggered an extensive research focus to find an innovative way to revalorize glycerol and transform to value-added chemicals. Yet, it is undeniably a necessary move towards achieving greener and sustainable processes. For instance, glycerol 1,2-carbonate (4-hydroxymethyl-1, 3-dioxolan-2-one) is currently one of the most celebrated glycerol derivatives that captured arising scientific and industrial attentions due to its extensive potential applicability. This cyclic ester of glycerol with carbonic …

Rambling Between "Zhong Yong" And "Catalysis", Zi-Dong Wei

Journal of Electrochemistry

“Zhong Yong” represents a traditional Chinese wisdom, which was first proposed by Confucius and continuously richened by his followers. “Zhong Yong” pursues the balances among all kinds of contradictions, and insists that neither “too much” nor “not enough” is good. For a successful catalyst, on which the adsorption of reactants must be not so strong and not so weak either. On this point of view, there are the same pursuits for “Zhong Yong” and catalysis. In this paper, the author starts his story with a conversation between Confucius and his student, followed by 3 interesting stories happening in the ancient …

Applying Bayesian Machine Learning Methods To Theoretical Surface Science, Shane Carr

McKelvey School of Engineering Graduate Student Theses & Dissertations

Machine learning is a rapidly evolving field in computer science with increasingly many applications to other domains. In this thesis, I present a Bayesian machine learning approach to solving a problem in theoretical surface science: calculating the preferred active site on a catalyst surface for a given adsorbate molecule. I formulate the problem as a low-dimensional objective function. I show how the objective function can be approximated into a certain confidence interval using just one iteration of the self-consistent field (SCF) loop in density functional theory (DFT). I then use Bayesian optimization to perform a global search for the solution. …

Interplays Of Co2, Subnanometer Metal Clusters, And Tio2: Implications For Catalysis And Co2 Photoreduction, Chi-Ta Yang

USF Tampa Graduate Theses and Dissertations

This research is motivated by two significant challenges facing the planet: reducing the emission of CO₂ to the atmosphere and production of sustainable fuels by harnessing solar energy. The main objective of this work is the study of promising photocatalysts for CO₂ reduction. DFT modeling of CO₂, subnanometer Ag&Pt clusters, and anatase TiO2 (101) surface is employed to gain fundamental understanding of the catalytic process, followed by validation using a guided experimental endeavor. The binding mechanism of CO₂ on the surface is investigated in detail to gain insights into the catalytic activity and to assist …

The Production Of Biobutanol From Biomass Via A Hybrid Biological/Chemical Process, Thomas Melvin Potts

Graduate Theses and Dissertations

Biobutanol use as a fuel began in the late 19th century. Problems remain in economic viability. A review of the state of the art and need for technical advances is presented.

The technical potential of producing biofuel from a naturally occurring macroalgae was studied. The algae grow in Jamaica Bay, New York City, in contaminated water. The process consisted of mechanical harvesting, drying, grinding, and acid hydrolysis to form an algal sugar solution. Clostridium beijerinckii and C. saccharoperbutylacetonicum were used in an acetone butanol ethanol (ABE) fermentation to make butanol. Fermentation was followed by distillation Butanol concentrations during fermentation reached …

A Metal-Free Approach To Biaryl Compounds: Carbon-Carbon Bond Formation From Diaryliodonium Salts And Aryl Triolborates, Kuruppu Lilanthi Jayatissa

Dissertations and Theses

Biaryl moieties are important structural motifs in many industries, including pharmaceutical, agrochemical, energy and technology. The development of novel and efficient methods to synthesize these carbon-carbon bonds is at the forefront of synthetic methodology. Since Ullmann’s first report of stoichiometric Cu-mediated homo-coupling of aryl halides, there has been a dramatic evolution in transition metal catalyzed biaryl cross-coupling reactions.

Our work focuses on the discovery and development of an unprecedented reagent combination for metal-free cross-coupling. It is hypothesized that direct carbon-carbon bond formation occurs via a triaryl-λ³-iodane and that electrophile/nucleophile pairing is critical for success in the reaction. Proof-of-concept …

The Synthesis Of Solid Supported Palladium Nanoparticles: Effective Catalysts For Batch And Continuous Cross Coupling Reactions, Kendra W. Brinkley

Theses and Dissertations

Catalysis is one of the pillars of the chemical industry. While the use of catalyst is typically recognized in the automobile industry, their impact is more widespread as; catalysts are used in the synthesis of 80% of the US commercial chemicals. Despite the improved selectivity provided by catalyst, process inefficiencies still threaten the sustainability of a number of synthesis methods, especially in the pharmaceutical industry. Recyclable solid supported catalysts offer a unique opportunity to address these inefficiencies. Such systems coupled with continuous synthesis techniques, have the potential to significantly reduce the waste to desired product ratio (E-factor) of the production …

Theoretical Investigation Of The Catalytic, Liquid-Phase Hydrodeoxygenation Of Organic Acids And Esters, Sina Behtash

Theses and Dissertations

With worldwide fossil fuel resources dwindling and greenhouse gas emissions rising, it is urgent to find renewable liquid fuel alternatives from e.g. biomass to meet the world’s growing energy demand. Lipid feedstocks and pyrolysis oils from woody biomass can be utilized for the production of second-generation biofuels via a catalytic hydrodeoxygenation (HDO) process. The conversion of fatty acids and esters plays an important role in the activity and selectivity of these processes. Understanding the HDO reaction mechanism of organic acids and esters on metal surfaces is a prerequisite for the rational design of new HDO catalysts specifically designed for upgrading …

The Catalysis Of Delayed Petroleum Coking, Anya M. Heinimann, Robert Khakimov, Hyun-Tae Hwang, Enrico N. Martinez

The Summer Undergraduate Research Fellowship (SURF) Symposium

Due to the decreasing crude oil quality (heavier crudes and increasing contaminant concentrations) methods for upgrading residues from the refining process, such as coking, are becoming increasingly important. Delayed coking, a method by which residues are thermally cracked (large heavy molecules broken into smaller lighter molecules), produces liquid products and solid coke which can both be sold for further profit. In order to increase the amount of liquid products produced since they are the most value added product of the coking process catalysts (platinum on 0.5% alumina and nickel (skeletal),molybdenum promoted (1 wt%)) were tested to see how they would …

Synthesis And Characterization Of Microporous And Mesoporous Catalysts For Shale Gas Upgrading, Danesh Contractor, Ravi Joshi, Rajamani Gounder

The Summer Undergraduate Research Fellowship (SURF) Symposium

The petroleum industry is gradually shifting from using naphtha to ethane as its feedstock and new ethane steam crackers are being built. Using ethane as a feedstock produces more ethene and less co-products such as propene, aromatics and C4 alkenes. Thus, the shift in feedstock will reduce the availability of these co-products. Developing methods for the interconversion of alkenes, and specifically using ethene as a reactant, can solve this problem.

This project focuses on synthesis and characterization of zeolites with the BEA framework topology, and their nickel exchanged versions as potential ethene dimerization catalysts. In future work, these materials will …

Reduction Of Ketoximes To Amines By Catalytic Transfer Hydrogenation Using Raney Nickel And 2-Propanol As Hydrogen Donor, Katherynne E. Taylor

Honors Theses

Ketoximes successfully underwent hydrogenolysis and hydrogenation under catalytic transfer conditions with Raney Nickel and 2-propanol as a hydrogen donor. Ketoximes were reduced to primary amines when 2% KOH was included in the reaction. In the absence of KOH N-isopropyl-secondary-amines were obtained in good yields.

Phenol Deoxygenation Over Hydrotreating Catalysts, Madelyn R B Ball

Honors Theses and Capstones

Phenol deoxygenation has been investigated as a model reaction for the deoxygenation of fatty acid methyl esters in biodiesel. Hydrodeoxygenated biodiesel is a drop-in fuel for petroleum diesel, and is a premium diesel with a high cetane number. As the first step in this research, two molybdenum catalysts were prepared, characterized and tested in a small-scale reactor. These catalysts were found to produce small amounts of benzene and cyclohexanol in the product stream, and confirmed the activity of the catalyst. A commercial cobalt molybdenum catalyst (Harshaw HT-400) was also tested and benzene, cyclohexanol, and cyclohexane were identified as products. Future …

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 …

Preparation Of Mesoporous Silica Supported Ruthenium Oxides And The Application And Kinetic Study In The Catalysis Of Water Oxidation, Yang Zhang

Open Access Dissertations

Photo-induced water splitting of water into H2 and O2 has been a major focus in the development of clean and renewable energy. The development of viable and efficient catalysts that facilitates O2 production remains the major challenge in the study of the corresponding half-reaction of water oxidation. There are plenty of metal oxides reported active in the catalysis of water oxidation. However, several important performance bench marks of those materials, such as the non-stoichiometric production of O2, slow reaction rate and/or low quantum efficiency, remain to be improved.

Ruthenium oxide (RuO2) has long been known as one of the most …

High-Pressure Vapor-Phase Catalytic Hydrodeoxygenation Of Lignin-Derived Compounds To Hydrocarbons On Bimetallic Catalysts In The Range Of 0.2-2.4 Mpa., Sara Lynn Yohe

Open Access Dissertations

Biomass, as the only renewable source of carbon, presents a sustainable alternative to liquid fossil fuels for the production of renewable transportation fuels and chemicals. The lignin portion of biomass poses a significant challenge in the upgrading and conversion of lignocellulosic biomass to fuels and chemicals, and in many current biorefineries is not utilized. However, the lignin fraction is a valuable feedstock due to its aromatic structure, lower O:C ratio than cellulose and hemicellulose, and high energy content (up to 40%) and weight fraction (average 25 wt%) of biomass. Several processes (including fast-pyrolysis, fast-hydropyrolysis, and liquid phase processing) are able …

Effect Of Nanoparticle Size, Support, And Potassium Dopant On Ruthenium Activity For Levulinic Acid (La) Hydrogenation To Γ-Valerolactone (Gvl), Shuo Cao

Theses and Dissertations

The purpose of this thesis is to study the effect of nano-particle size, support and potassium dopant on ruthenium activity on the levulinic acid (LA) hydrogenation to ã-valeroactone (GVL).In hydrogenation reaction, H2 as the gas phase reactant reacts with the metal atoms at the surface of particle size, thus a high level of metal dispersion is critical to maximize the amount of atoms on the surface. This reaction has been widely investigated by varied metal supported catalysts and proved that Ru is the most active metal for it. However, most of researchers only focused on the reaction pathway, rather than …

Model Pt- And Pd-Based Electrocatalysts For Low Temperature Fuel Cells Applications, Selasi Ofoe Blavo

USF Tampa Graduate Theses and Dissertations

In the search for alternative energy technologies, low temperature fuel cells continue to feature as technologies with the most promise for mass commercialization. Among the low temperature fuel cells, alkaline and proton exchange membrane fuel cells are the most popular. Alkaline fuel cells have typically been used for water generation as well as auxiliary power for space shuttles. Their bulkiness however makes them undesirable for other applications, especially in automobiles, where there is a great demand for alternative technologies to internal combustion engines. Proton exchange membrane fuel cells on the other hand possess numerous qualities including their compact size, high …

Homogeneous Viologens For Use As Catalysts In Direct Carbohydrate Fuel Cells, Dane C. Hansen

Theses and Dissertations

Deriving electrical energy from glucose and other carbohydrates under mild conditions is an important research objective because these biomolecules are abundant, renewable, and can provide 12 to 24 electrons per molecule, yielding substantial electrical power. It was previously observed that disubstituted viologens, salts of N,N'-disubstituted 4,4'-bipyridine, are able to oxidize glucose under alkaline conditions. Building on that initial result, the objective of this work was to understand and quantify the effectiveness and utility of viologens as catalysts for use in direct carbohydrate fuel cells.The extent that viologens oxidize carbohydrates, the conditions under which that oxidation occurs, and the mechanism for …

Synthesis, Characterization, And Testing Of Atomically-Precise Au Clusters Supported On Tio₂ For Co Oxidation, Sarthak Gaur

LSU Doctoral Dissertations

Supported Au catalysts have been studied extensively for CO oxidation. These catalysts are known to catalyze this reaction even at sub-ambient temperatures. While recent literature demonstrates catalytic activity of gold nanoparticles <2 nm, the next stage in fine tuning this catalysis process is to develop gold clusters prepared with atomic precision. Such atomically precise gold catalysts supported on TiO2 hitherto have not been investigated for CO oxidation. The main objective of this work is to synthesize atomically-precise Au38 clusters in a flask-based method using principles of wet chemistry, to characterize these clusters using various advanced spectroscopic techniques, and to test these clusters as potential catalytic materials for CO oxidation. Furthermore, we have tested TiO2-supported Au38 clusters and a commercially purchased Au/TiO2 catalyst for CO oxidation at 30 °C and 60 °C, and used DRIFTS as a probe spectroscopic technique to correlate kinetics with the mechanism occurring on the surface of both catalysts in order to device the mechanistic pathways for CO oxidation. The work reported in this dissertation is the first spectroscopic observation of the phenomena where sulfur may have beneficial effect on the catalytic activity of Au/TiO2 catalysts. Such an interesting observation where sulfur has beneficial effect on catalytic activity of Au/TiO2 catalysts has never been observed in the past. We have also synthesized and tested Fe3O4@Au core-shell nanoparticles supported on TiO2 for CO oxidation. We show for the first time that, core-shell type nanogold catalysts are better suited compared to pure gold nanoparticles for heterogeneous gas phase catalysis of CO oxidation. By conducting comprehensive experiments towards understanding CO oxidation catalysis using X-ray photoelectron spectroscopy, infrared spectroscopy, and temperature programmed reduction, we show that the enhanced catalytic activity is due to a combination of factors ranging from synergistic interaction between Au and Fe, complete removal of organic capping ligands and the presence of metallic gold (Au0) in the active catalyst.