Catalysis and Reaction Engineering Commons^™

Applications For The Quasi-Atomic Orbital And Constrained Density Functional Theory Methods On Catalytic Reactions, Alvaro David Loaiza Orduz

LSU Doctoral Dissertations

Selective activation of C–O, C–H, and C–C bonds underpins biomass upgrading, alkane functionalization, and CO₂ conversion. Despite their importance, the electronic factors governing catalytic performance remain incompletely understood, and many industrial processes still rely on empirical trends or material-specific observations. This dissertation addresses this gap by applying density functional theory (DFT), thermodynamic decomposition, and electronic-structure analysis to identify unifying principles of reactivity across transition-metal phosphides, vanadate oxides, copper-based electrocatalysts, and mixed IrO₂–RuO₂ layers. This work examines how charge transfer, orbital localization, and ligand-induced perturbations control reaction pathways in diverse catalytic systems. C–O bond scission in 2-methyltetrahydrofuran (MTHF) and methanol was …

Low Temperature Methane Coupling With Co And Co2, A K M Kazi F.M. Aurnob

LSU Doctoral Dissertations

Methane is the smallest hydrocarbon and the most abundant component in natural gas. Despite its availability, its chemical utilization has remained limited due to the challenges associated with direct methane activation and conversion. Most of the methane oxidation and oxidative carbonylation reactions in literature have been carried out at high-pressure using batch reactors or at ambient pressure using flow reactors. While batch reactors have been shown to have higher product yields, they are limited in their capability to provide real-time kinetic insights and comprehensive mechanistic understanding of the reactions involved due to the long residence time. This limits rationalization of …

Sustainable Aviation Fuel Production From Plastic Waste On Bifunctional Catalysts, Kamryn Culp

Williams Honors College, Honors Research Projects

Catalytic hydrocracking was studied as a chemical recycling method for converting mixed plastic polypropylene (PP) and polyvinyl chloride (PVC) waste into sustainable aviation fuel-range hydrocarbons. Addressing both plastic pollution and aviation-related CO₂ emissions, bifunctional Ni- and Pt-based catalysts supported on Al₂O₃ and TiO₂ were evaluated under 30 bar hydrogen pressure at 250 °C. The inclusion of PVC, often regarded as a catalyst poison due to chlorine content, was examined at 1 wt% and 5 wt% to assess catalyst tolerance to it and resulted performance. Reaction rates and product selectivity were analyzed using gas chromatography. Results show that Ni/TiO₂ outperformed other …

Effects Of Polyolefin Types On Catalytic Hydrocracking, Kenneth Jackson Seeber

Williams Honors College, Honors Research Projects

Plastic waste recycling has become an important conversation in the last couple of decades with pollution on the rise. One of the few ways to recycle plastics is by breaking these long-chained polymers down via catalytic processes. Due to many plastic products being a blend, it is imperative that any chosen catalyst that could be used for recycling should be able to handle different types of polymers. This paper discusses how tungsten carbide over silica (W_xC/SiO₂) catalyzes the degradation of a few selected polymers and polymer blends. From this research it was determined that W_{x …}

The Roles Of Carbonaceous Wastes For Catalysis, Energy, And Environmental Remediation, Chi Huey Ng, Mohd Aizzan Mistoh, Siow Hwa Teo, Andrea Galassi, Hin Taufiq-Yap, Nancy Julius Siambun, Jurry Foo, Coswald Stephen Sipaut, Jeffrey Seay, Jidon Janaun

Chemical and Materials Engineering Faculty Publications

This article reviews recent studies about various generations of the carbon materials for their applications in energy and environmental remediation. The synthesis routes of the carbon materials including the condition parameters, interaction of precursors, dopants and carbon materials, as well as their physical/chemical properties are explicated first. Then, the application and mechanism of metal-free/metal-doped/non-metal-doped carbon materials are discussed in detail. Lastly, this review is ended with a summary and invigorating perspectives on the challenges and future directions at the forefront of the catalysis platform to take a step further for real application.

Change Of Metal Oxidation State At High Temperature, Impact Of Temperature And Reactive Gases, Yegor Nikitin

Dissertations and Theses

The fundamental understanding of gas-solid reactions enables a wide range of applications to be developed and improved. Specifically, the use of metal-based materials is critical to ensuring robust, safe, and long-term operations. For example, in power systems where boilers are used to generate steam for heat or electricity generation the use of stainless metal alloys is critical to allow high quality steam to be produced in a very harsh environment. Alternatively, in catalysis, the use of metal doped heterogeneous catalysts are essential in achieving selectivity and conversion performance for chemical synthesis to emissions abatement. Typically, these metal alloys must withstand …

Computationally-Driven Insights Into The Ligand Environments Of Materials For Catalysis And Separations, Stephen Vicchio

All Dissertations

Designing new catalytic and sorption materials is necessary to limit global temperature rise below 1.5 ◦C by 2050, while also meeting global energy demands. Climate change and energy production are not mutually exclusive; global population growth has direct impacts on global energy demands and climate. In both catalysis and adsorption applications, new technologies are needed to address these challenges. Catalysis can provide alternate, low-energy routes for converting low-value gases into higher-value chemical commodities, thus altering our current energy production. Likewise, new sorption materials can capture previously emitted CO₂ from decades of energy production from fossil fuels, thus helping to …

Bimetallic Compound Catalysts With Multiple Active Centers For Accelerated Polysulfide Conversion In Li-S Batteries, Wu-Xing Hua, Jing-Yi Xia, Zhong-Hao Hu, Huan Li, Wei Lv, Quan-Hong Yang

Journal of Electrochemistry

Practical applications of lithium-sulfur (Li-S) batteries are hindered mainly by the low sulfur utilization and severe capacity fading derived from the polysulfide shuttling. Catalysis is an effective remedy to those problems by promoting the conversion of polysulfides to reduce their accumulation in the electrolyte, which needs the catalyst to have efficient adsorption ability to soluble polysulfides and high activity for their conversion. In this work, we have proposed a bimetallic compound of NiCo₂S₄ anchored onto sulfur-doped graphene (NCS@SG) to fabricate a catalytic interlayer for Li-S batteries. Compared to CoS, the NiCo₂S₄ demonstrated much higher …

Ambient Ammonia Synthesis Via Microwave-Catalytic Materials And Plasma Chemistry, Siobhan Brown

Graduate Theses, Dissertations, and Problem Reports (ETD)

Ammonia is critical to supporting human life on earth because of its use as fertilizer. The Haber-Bosch process to produce ammonia has been practiced for over 100 years. This process operates at high pressure and temperature to overcome the thermodynamic and kinetic limitations of the ammonia synthesis reaction thus researchers have tried to overcome it for decades. At present this process represents 1% of global energy usage and 2.5% of global CO₂ emissions. The proposed chemical looping ammonia synthesis approach seeks to reduce the environmental impact of this critical process and to elucidate microwave-catalytic principles.

This research aims to …

Elucidation Of Active Site And Mechanism Of Metal Catalysts Supported In Nu-1000, Hafeera Shabbir

All Dissertations

Advances in extraction of shale oil and gas has increased the production of geographically stranded natural gas (primarily consisting of methane (C1) and ethane (C2)) that is burned on site. A potential utilization strategy for shale gas is to convert it into fuel range hydrocarbons by catalytic dehydrogenation followed by oligomerization by direct efficient catalysts. This work focuses on understanding metal cation catalysts supported on metal-organic framework (MOF) NU-1000 that will actively and selectively do this transformation under mild reaction conditions, while remaining stable to deactivation (via metal agglomeration or sintering). I built computational models validated by experimental methods to …

Surface Structure Engineering Of Feni-Based Pre-Catalyst For Oxygen Evolution Reaction: A Mini Review, Jia-Xin Li, Li-Gang Feng

Journal of Electrochemistry

Nitrite, a widespread raw material, is harmful to human health for long-term consumption. At present, the detection methods of nitrite mainly include chemical analysis, fluorescence, ultraviolet spectrophotometry and chromatography. These methods have ideal sensitivity and selectivity, but also have some characteristics: cumbersome operation, expensive equipment and professional personnel. Therefore, the development of a simple and sensitive nitrite assay is of great significance. In this paper, the Au/rGO/FeOOH composite materials, which revealed good synergistic catalytic performance among the three elements in the composite, were prepared by simple hydrothermal method and reduction method for the first time with large specific surface area …

Modeling Solvent Extraction Of Lignin From Hardwoods, Su Pan

McKelvey School of Engineering Graduate Student Theses & Dissertations

This study interprets the observed behavior of solvent extraction of lignin from hardwoods by adapting the framework of the FLASHCHAIN theory (Niksa and Kerstein, 1991; Niksa, 2017). A constitution submodel specifies distributions of molecular weight and reactive sites for native lignin. The model simulates delignification as depolymerization of lignin macromolecules into fragments small enough to be soluble. This process competes with intrachain condensation that consumes labile bridges without forming new fragments, and with recombination that forms larger chains and inhibits further depolymerization. After the soluble fragments are transported from the particle into the bulk solvent, all chemistry continues as long …

Engineering Lewis Acidic Materials For Biomass Conversion And Battery Applications., Md Anwar Hossain

Electronic Theses and Dissertations

My long-term goal is to develop catalytic systems to produce renewable energy for a sustainable society. The overall research objective of my dissertation is to advance understanding of Lewis acidic materials for (1) conversion of renewable lignin into phenolics and (2) enhanced cycling stability of lithium metal batteries to safely store renewable electricity from wind and solar, thereby laying the groundwork for our transition to a sustainable society. Petroleum is a conventional feedstock for current transportation fuels (gasoline, diesel, and jet fuels). However, petroleum is a finite resource and produces greenhouse gases (CO₂ and CH₄) upon processing, …

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, …

Microwave-Assisted Carbon Nanotube Growth From Methane On Surface Catalyst Exsolving Perovskite Oxide, Angela M. Deibel

Graduate Theses, Dissertations, and Problem Reports (ETD)

The novel method of using a perovskite exsolution catalyst, strontium titanium nickel oxide (STNO), proved capable of simultaneously producing carbon nanotubes (CNTs) and CO_x-free hydrogen during methane decomposition under microwave irradiation. An optimization of common perovskite materials was conducted for microwave-responsiveness with the results reported in this study. Out of the materials screened, strontium titanium nickel oxide (STNO) was the best candidate to achieve an acceptable methane conversion rate as well as a decent responsiveness to microwave. STNO was further optimized through Ni content, reduction dwell time, and reduction temperature to produce the best methane conversion and CNT …

Modified Electrode Surfaces With Hydrogen Evolution Reaction Catalysts Derived From Electropolymerized Complexes With Redox Active Ligands., Amanda Mae Arts

Electronic Theses and Dissertations

The demand for energy is growing exponentially, and to keep up with these demands new technologies for renewable energy have received increased attention. Hydrogen is one of the most promising energy sources for the future and plays a vital role in water electrolysis and fuel cells, as the hydrogen evolution reaction (HER) is the main step in the water splitting process. To increase the reaction rate and improve efficiency for the water electrolysis, catalysts are used to minimize the overpotential.

Most of the current electrocatalysts for HER are heterogeneous in nature and are dominated by platinum and other precious metals …

Continuous Preparation And Application Of Novel Heterogeneous Catalysis, Michael B. Burkholder

Theses and Dissertations

Transition metal heterogeneous catalysts are widely used across many chemical industries to reduce waste and emissions and reduce production time while increasing rate. The prevalence of these materials results from the complex relationship between metal nanoparticles and supports affecting final catalytic performance. Rational catalyst synthesis describes the ability to precisely engineer structures through controlled preparation. Novel materials and continuous processing represent a promising approach for rational catalyst synthesis.

The application of these catalysts in continuous, multiphase processes, such as cross-coupling reactions, oxidation chemistry, and nitroreduction processes, are paramount to developing new commercial routes for high-value products. Pd/G catalysts synthesized by …

Simultaneous Activation Of Stable Molecules- Methane And Nitrogen- Using Microwave Reactor With And Without Plasma- To Produce Ethylene And Ammonia, Sarojini Tiwari

Graduate Theses, Dissertations, and Problem Reports (ETD)

The discovery of stranded natural gas around the world has made shale gas cheaper and widely accessible. This has driven the relevant research towards the direct utilization of Methane (CH4), a major component of natural gas. CH4 is a highly stable molecule, hence its activation and consequent formation of value-added chemicals in a direct and efficient manner is a relevant problem of the 21st century. All the commercial processes convert natural gas to chemicals indirectly, via the formation of syngas followed by several reactions. The conventional systems are energy intensive and one of the major contributors to green-house gas emissions. …

Microwave-Assisted Natural Gas Conversion To Value-Added Chemicals, Xinwei Bai

Graduate Theses, Dissertations, and Problem Reports (ETD)

Stranded gas is a raw gas mixture of volatile hydrocarbons where the main composition is methane. The producers flare the stranded gas at the site because the cost of collecting and transporting the gas is higher than the value of the gas itself. To reduce the waste of this natural resource, it is worthwhile to utilize the on-site stranded natural gas as feedstock to produce value-added chemicals without emitting greenhouse gas. Direct natural gas conversion process is more desirable because of lower capital investment. Methane and ethane, the two major components of natural gas, are very stable molecules that usually …

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. …

Engineering Dopant Position In Structure-Controlled Ceo2-Zro2 Catalysts, Behnam Safavinia

LSU Master's Theses

CeO₂-ZrO₂ (CZO) nanoparticles (NPs) have application in many catalytic reactions, such as methane reformation, due to their oxygen cycling ability. Ni doping has been shown to improve the catalytic activity and acts as an active site for the decomposition of methane. In this work, Ni:CZO NPs were synthesized via a two-step co-precipitation/molten salt synthesis to compare Ni distribution, oxygen vacancy concentration, and catalytic activity relative to a reference state-of-the-art catalyst. To better understand the effects of Ni position and dispersion, and oxygen vacancy formation in these materials, the Ni concentration, reaction time, and deposition methods were varied. …

Nanostructured Metal Thin Films As Components Of Composite Membranes For Separations And Catalysis, Michael J. Detisch

Theses and Dissertations--Chemical and Materials Engineering

Novel metallic thin film composite membranes are synthesized and evaluated in this work for improved separations and catalysis capabilities. Advances in technology that allow for improved membrane performance in solvent separations are desirable for low molecular weight organic separation applications such as those in pharmaceutical industries. Additionally, the introduction of catalytic materials into membrane systems allow for optimization of complex processes in a single step. By adding a nanostructured metallic thin film to its surface, a polymer membrane may be modified to exhibit these improved properties. Using magnetron sputtering, thin metal films may be deposited on commercially available membranes to …

A Study Of Protein And Peptide-Directed Nanoparticle Synthesis For Catalytic Materials, Abdollah Mosleh

Graduate Theses and Dissertations

Nanoparticles have received much attentions due to their unique properties that makes them suitable candidates for a broad range of applications. As the size of particles decreases, their surface area-to-volume ratio would increase which is the main cause of much attention. In addition to the size, their morphologies and compositions may also play important roles for defining unique properties. Nanoparticle synthesis include both bottom-up and top-down strategies. To control the process of inorganic nanoparticles synthesis one could follow the bottom-up approach to have atom-level control over their compositions, morphologies, phases, and sizes which is the subject of this work. Due …

Development Of A Ws2 Catalyst For Hydrogen Evolution And Improvement Via Platinum Nanoparticle Decoration, Alexander O'Brien

Chemical Engineering Undergraduate Honors Theses

In response to a growing global need to improve utilization of green energy, the concept of renewable energy storage via electrolytic hydrogen production has gained popularity in recent years. However, the prohibitive expense of the bulk platinum catalysts currently used for the hydrogen evolution reaction prevents such a concept from being widely adoptable. This research focuses on a possible alternative catalyst, nanolayer WS₂, which is capable of promoting the hydrogen evolution reaction while maintaining economic viability. Bulk WS₂ was prepared in semiconducting, nanolayer form through liquid phase exfoliation. Prepared catalyst inks consisting of this material demonstrated successful …

Elucidation Of The Catalytic Partial Oxidation Of Methane Utilizing The One-Of-A-Kind Catalytic Shock Tube Technique, Robyn E. Smith

Dissertations and Theses

The mechanism for the catalytic partial oxidation of methane has been debated in scientific literature for over 20 years. This is a seemingly simple reaction producing CO, CO₂, H₂ and H₂O through either partial oxidation followed by complete oxidation or complete oxidation followed by reforming steps. What is happening when the reaction is allowed to occur in an environment absent of transport limitations, absent of temperature gradients and temperature changes, absent of boundary layers must be understood and, until now, has yet to be achieved in one experimental technique.

A novel method using a one …

First-Principles Study On The Catalytic Role Of Cerium Dioxide In The Conversion Of Organic Compounds, Chuanlin Zhao

LSU Doctoral Dissertations

Ceria is an earth-abundant material that has been widely used in heterogeneous catalysis, environmental catalysis, and energy applications thanks for its ability to readily convert between different oxidation states. The objective of this study is to theoretically elucidate the reaction mechanisms for the conversion of model organic compounds on ceria, in order to gain insights for the design of cost-effective and selective ceria-based catalysts. Acetaldehyde, acetic acid, and para-nitrophenyl phosphate monoester were selected as the model compounds to probe ceria surfaces. Density functional theory calculations can provide accurate predictions of adsorption and reaction energetics, which can be used to …

Investigation Of The Effects Of Solid-State Treatments On The Structure And Mobility Of Copper In Zeolites, Jiayang Wu, Laura Wilcox, Rajamani Gounder

The Summer Undergraduate Research Fellowship (SURF) Symposium

Zeolites are microporous, aluminosilicate catalysts that play an important role in industrial applications as well as studies for the fundamental understanding of catalysts for emerging reactions of interest. The introduction of aluminum into the zeolite lattice introduces a negative charge on the framework that can be balanced with extra-framework cations. The control of the aluminum distribution and the choice of charge balancing cations allows for the ability to tailor the active sites to facilitate a desired reaction. This research focuses on studying copper active sites in zeolites. Copper oxide was used as a copper precursor to introduce copper ions in …

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 …

Assembling Of Niox/Mwcnts-Gc Anodic Nanocatalyst For Water Electrolysis Applications, Islam M. Al-Akraa Dr., Yaser M. Asal Mr, Saher D. Khamis Eng

Chemical Engineering

Glassy carbon (GC) electrode is intended to be modified with nickel oxide (NiOx) and multiwalled carbon nanotubes (MWCNTs) in the anodic reaction of water electrolysis. NiOx deposition time is optimized and a 5 min was enough to attain the maximum activity. A further modification of the catalyst with MWCNTs could greatly enhance its stability during continuous electrolysis. As an outcome, an energy amount of 21.7 kWh/KgO2 is minimized. Several electrochemical and materials characterization setups will be utilized to test the catalyst activity and to know its geometry and structure.

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 …