Engineering Commons^™

Alternative View Of Oxygen Reduction On Porous Carbon Electrocatalysts: The Substance Of Complex Oxygen-Surface Interactions, Giacomo De Falco, Marc Florent, Jacek Jagiello, Yongqiang Cheng, Luke L. Daemen, Anibal J. Ramirez-Cuesta, Teresa J. Bandosz

Publications and Research

Electrochemical oxygen reduction reaction (ORR) is an important energy-related process requiring alternative catalysts to expensive platinum-based ones. Although recently some advancements in carbon catalysts have been reported, there is still a lack of understanding which surface features might enhance their efficiency for ORR. Through a detailed study of oxygen adsorption on carbon molecular sieves and using inelastic neutron scattering, we demonstrated here that the extent of oxygen adsorption/interactions with surface is an important parameter affecting ORR. It was found that both the strength of O2 physical adsorption in small pores and its specific interactions with surface ether functionalities in the …

Bio-Inspired Materials For Electrochemical Sensors, Matthew Joseph Hummel

Electronic Theses and Dissertations

Electrochemical biosensors are a rapidly growing research area that has greatly improved its specificity, accuracy, and precision in the detection of biomolecules in contemporary literature and industry alike. Typically, these systems exist in a three-electrode conformation with a working electrode functioning as the anode, a counter electrode functioning as the cathode, and a reference electrode allowing for the control of potential in the system. The method by which these sensors work is through the sharing of electrons via redox reactions with the target molecule and the working electrode or modifications on its surface. By exploiting the function of biomaterials that …

Studying The Effects Of New Additive Materials For The Improvement Of The Capacity And Cycle Life Performance Of The Lead-Acid Battery, Julian Kosacki

Doctoral Dissertations

"Lead-acid batteries are an established technology with nearly 99% recyclability; however, lead-acid batteries produce only 40% of their theoretical capacity due to poor active mass utilization and PbSO4 pore blockage, and the longevity of the batteries is hampered by secondary reactions during the cycle life such as corrosion and gassing.

Lead-acid batteries were investigated and improved through several different approaches: an alternative electrolyte to mitigate secondary reactions, graphite additives to improve positive active mass (PAM) utilization, and dispersant additives to help the industrial pasting process.

The thermodynamics and chemical reactions of a commercial electrolyte replacement called Tydrolyte^TM were investigated …

Investigation Of Iron-Nickel Based Nanoparticles As Catalysts For Oxygen Evolution Reaction (Oer), Prashant Acharya

Graduate Theses and Dissertations

Hydrogen fuel is increasingly seen as an appealing alternative by both the scientific and the industrial communities in the drive towards a clean energy future. Hydrogen, unlike fossil-based fuels, does not release carbon dioxide, a chief component of greenhouse gases, upon combustion. However, more than 95% of the hydrogen in the world is still produced by burning fossil fuels as this method is currently the only economically feasible option at a large industrial scale.

Water electrolysis shows a lot of potential in both hydrogen generation and in the storage of energy from renewable sources such as wind and sunlight. Likewise, …

Carbon Capture And Utilization, Sriram Valluri

Dissertations, Master's Theses and Master's Reports

As the world moves towards clean energy initiative, carbon capture and utilization technologies are key to achieving net zero emissions. CO2 capture with amines has many disadvantages and cannot be applied to commercial power plants. The current manuscript will address this issue as well as a solution that involves the use of low-cost alkali absorbent CO₂ capture solutions, combined with an electrochemical regeneration method that uses the least amount of energy available for capture and regeneration. This research will also further address the issue of how to deal with the captured CO2. Several viable storage and utilization methods have …

Cold Plasma Enhanced Active Sites On Supported Nip Nanoparticles For The Oxygen Evolution Reaction, Michael Ricci

Williams Honors College, Honors Research Projects

Identifying materials to efficiently facilitate the oxygen evolution reaction (OER) is key to advancing water electrolysis, an essential technology in the pathway towards a sustainable energy future. Here, we explore cold-plasma treatment as a facile method to enhance the activity of NiP nanoparticles supported on activated carbon. NiP nanoparticles were synthesized on an activated carbon support using a solid-state method and were then treated with argon, oxygen, and hydrogen plasmas for extended times. In all cases, plasma treatment reduced the number of active sites on the support. OER activity was evaluated by testing the materials in alkaline conditions. The activities …

Biomass-Derived Electrode Materials And Sustainable Processes For Supercapacitors, Katelyn M. Shell

Theses and Dissertations

Biomass is one of the most abundant natural resources and has been used as a source of energy for thousands of years. Biomass as a precursor for energy storage materials is still relatively novel and faces several obstacles before becoming commonly used in today’s electrical devices. Currently, energy storage devices, such as batteries, capacitors, and supercapacitors, utilize petroleum-derived graphitic carbons for anodes, generating a need for more sustainable materials. Biomass, as a carbon-rich source for electrode materials, presents a viable and economically feasible alternative due to the prevalent lignocellulosic compounds: lignin, cellulose, and hemicellulose. Preliminary studies on the solid residues …

Enhanced Kinetics And Modeling Of Pan-Based Carbon Felt Anodes In Vanadium Redox Flow Batteries, Michael Cyrus Daugherty

Doctoral Dissertations

All-vanadium redox flow batteries (VRFBs) are a promising technology for grid-level energy storage, however, there are still several limitations in the forms of durability, efficiency, and overall costs, which are barriers to its commercial viability. With both bulk electrolyte flowing through its porous matrix and species flux at the solid-electrolyte interface, electrodes are the component of VRFB systems which host electrochemical reactions and facilitate contact between the liquid phase electrolyte and the electronically conductive solid phase. While the more limiting electrode in VRFB systems is dependent on the material, for polyacrylonitrile (PAN)-based carbon felts, the anode constitutes a larger portion …

Mxenes As Flow Electrodes For Capacitive Deionization Of Wastewater, Naqsh E. Mansoor

Boise State University Theses and Dissertations

The energy-water nexus poses an integrated research challenge, while opening up an opportunity space for the development of energy efficient technologies for water remediation. Capacitive Deionization (CDI) is an upcoming reclamation technology that uses a small applied voltage applied across electrodes to electrophoretically remove dissolved ionic impurities from wastewater streams. Similar to a supercapacitor, the ions are stored in the electric double layer of the electrodes. Reversing the polarity of applied voltage enables recovery of the removed ionic impurities, allowing for recycling and reuse. Simultaneous materials recovery and water reclamation makes CDI energy efficient and resource conservative, with potential to …

Brominated Carbon Materials As Positive Electrodes For Nonaqueous Secondary Lithium-Bromine Batteries, Benjamin Beau Peterson

LSU Doctoral Dissertations

Secondary lithium-bromine (Li-Br₂) batteries have theoretical potentials near 4.1 V vs Li/Li⁺ and capacities more than 2 times greater than conventional Li-ion batteries. Herein, secondary, non-aqueous Li-Br₂ half-cell batteries are reported using a Li metal anode, carbon-coated glass fiber separator, non-aqueous Li-based electrolytes with and without the addition of lithium bromine (LiBr) salt, and positive electrodes consisting of either chemically brominated non-graphitic carbon or carbon derived from the carbonization of metal-organic frameworks (MOFs) with LiBr embedded into the micro- and mesopores of the carbon matrix. The separator is effective in mitigating the transport of Br_{2 …}

Engineering Ionomer Materials For Addressing Ohmic Resistances In Electrochemical Desalination And Waste Heat Recovery, Varada Menon Palakkal

LSU Doctoral Dissertations

Water scarcity and energy availability present important challenges that need to be addressed in the coming centuries. In the front of water technologies, desalting brackish water is of extreme importance for thermal electric power plants, chemical manufacturing plants, and other industrial operations that treat and reuse their water utilities. Membrane capacitive deionization (MCDI) is an energy efficient desalination technique that has drawn attention from commercial entities. Most material research studies on MCDI focus on enhancing electrode performance while little emphasis is given to rationale design of ion-exchange membranes (IEMs). In this work, the ionic conductivity, permselectivity, and thickness for three …

Theoretical Investigation Of Fundamental Cathode Processes In Metal-02 Batteries, Saurin Hiren Rawal

LSU Doctoral Dissertations

In this thesis we theoretically explore the different fundamental phenomena associated with metal-air batteries (where the metal can be Li, Na or K) using first principles density functional theory. We start by investigating the adsorption of the starting reactants/primary intermediates i.e. metal superoxides and superoxide anion on Au(111) and Au(211). We elucidate the influence of electric fields and the importance of including explicit solvents on the adsorption energy of these intermediates. We show that these effects are considerable and should be included for future reaction modeling of these batteries. Following this we investigate the reaction of M⁺ and O …

Multi-Component Material For Solar Energy Conversion And Fundamentals Of Lead Acid Batteries, Crystal Ferels

Graduate Research Theses & Dissertations

Synthesis of complex inorganic materials is desirable because their complex composition allows more degrees of freedom and tunability, whose properties differ from their parent components. As an expansion on this concept, we synthesized a quinary compound Ce3FeWS3O6, using a molten flux method and a solvothermal method. The compound crystallizes into a hexagonal crystal system with space group P63/m. Its electric partition shows an anion with the form [(Ce3+)3W6+(S2-)3(O2-)6]3- forcing the transition metal Fe3+ state and leaving no conduction electrons, making the material a semiconductor. This compound is the right candidate as photoelectric material capable of absorbing photons from the solar …

Transition Metal Chalcogenide Hybrid Systems As Catalysts For Energy Conversion And Biosensing, Siddesh Umapathi

Doctoral Dissertations

"Generation of hydrogen and oxygen through catalyst-aided water splitting which has immense applications in metal air batteries, PEM fuel cells and solar to fuel energy production, has been one of the critical topics in recent times. The state of art oxygen evolution reaction (OER), oxygen reduction reaction (ORR), hydrogen evolution reaction (HER) catalysts are mostly comprised of precious metals. The current challenge lies in replacing these precious metal-based catalysts with non-precious earth-abundant materials without compromising catalytic efficiency.

This research explores mixed metal selenides containing Fe-Ni, Fe-Co and RhSe which were hydrothermally synthesized and/or electrodeposited and tested for OER and ORR …

Application Of Immobilized Palladium Monolithic Catalysts In Suzuki-Miyaura And Tsuji-Wacker Redox Reactions, Sajjad Ghobadi

Theses and Dissertations

Herein, a wholistic analysis of the viability of monolithic catalysts for redox reactions is presented. The interdisciplinary approach taken in this systematic study included preparation and investigation on Pd-on-carbon monoliths as catalysts in a flow and electrochemical settings.

The Suzuki-Miyaura reaction-focused study led to rational design, preparation, and successful application of Pd⁰-on-graphene oxide (GO) monolithic catalysts in flow conditions. In this study a combination of chemical reduction, freeze-casting, and vapor-phase reduction processes was applied to Pd-GO structures leading to the preparation of these monoliths. The Suzuki flow synthesis reactions revealed that the monolithic structure led to significantly improved …

Anion Exchange And Bipolar Membranes For Electrochemical Energy Conversion And Storage, Zhongyang Wang

McKelvey School of Engineering Theses & Dissertations

Anion exchange and bipolar membrane fuel cells generate electrical energy directly from chemical fuels and have attracted considerable interests as alternate power sources for large market applications, such as transportation (hydrogen fuel cells) and unmanned vehicles (sodium borohydride fuel cells). Anion exchange membrane (AEM), generally composed of a polymer with covalently tethered ionic groups, is the central component of the fuel cell serving as the electrolyte, conducting hydroxide ions from cathode to anode, where fast ionic conduction is directly related to power output. However, AEMs currently used in fuel cells (H2 fuel cells and sodium borohydride fuel cells) exhibit ion …

Design, Microfabrication And Characterization Of Concentric Gold Nanoring Electrode For Neurochemical Sensing, Haocheng Yin

Doctoral Dissertations

Nanoelectrodes have become widely used in electrochemical sensing in recent decades. When compared to microelectrodes, it has many unique advantages such as high signal to noise ratio, small sample volume requirement, and lower detection limits.

This work reports on the microfabrication and characterization of a gold nanoring electrode (Au NRE) patterned on top of a silicon (Si) micropillar. An NRE of 165  10 nm in width was micropatterned on 4.6  1 µm diameter  17.5  2.5 µm long Si micropillar with an intervening 50 nm thick hafnium oxide insulating layer. Scanning electron microscopy and energy dispersive spectroscopy …

Modification And Optimization Of Conducting Polymer-Modified, Redox-Magnetohydrodynamics (R-Mhd) Pumping For Enhanced And Sustained Microfluidics Applications, Md Foysal Zahid Khan

Graduate Theses and Dissertations

In this work, a novel microfluidic pumping approach, redox-magnetohydrodynamics (R-MHD) has improved by materials and device optimization to use in lab-on-a-chip applications. In R-MHD, magnetic flux (B) and ionic current density (j) interacts to generate body force (FB) in between active electrodes, according to the equation FB = j×B. This unique fluid pumping approach is scalable, tunable, generates flat flow profile, and does not require any channels or valves. Pumping performance, such as speed scales with the ionic current density (j) and duration depends on the total charge (Q). The ionic current density (j) results from the conversion of electronic …

Recent Advances In Nanofluidic Electrochemistry For Biochemical Analysis, Zhong-Qiu Li, Zeng-Qiang Wu, Xing-Hua Xia

Journal of Electrochemistry

Nanofluidics, as a young research field, has been receiving more and more attentions. It has been successfully applied in various fields including nanoscale separation, biochemical sensing and energy conversion. The development of nanofluidics is closely related to electrochemistry that can provide a driving force for the study of the material transport characteristics in nanopores/nanochannels. On the other hand, nanopores/nanochannels can creat a microenvironment for study of spatially nanoconfined electrochemistry. The combination of nanofluidics and electrochemistry has given rise to many new theories and technologies for single molecule/particle analysis and nanofluid manipulation. Herein, we provide a review of the recent progresses …

A Low Noise Temperature Control System For Nanopore-Based Single Molecule Analysis, Cheng-Yu Yang, Zhen Gu, Zheng-Li Hu, Yi-Lun Ying, Yi-Tao Long

Journal of Electrochemistry

Nanopore employs a single bio-molecule interface, which is a highly sensitive single-molecule detection technology for measuring single biomolecules such as DNA, RNA, protein, and peptide. The interaction between single molecule and nanopore is thermodynamically controlled. Therefore, it is urgent to precisely control the temperature of the nanopore system without introduction of any noise. In this paper, we have developed a low-noise temperature control system for single-molecule detection of nanopores to achieve precise regulation at the ambient temperature during measurements. The system utilizes the thermoelectric effect of the semiconductor refrigerating chip to heat or cool the detection chamber, while adopts electromagnetically …

Single Particle Impact Electrochemistry: Analyses Of Nanoparticles And Biomolecules, Jian-Hua Zhang, Yi-Ge Zhou

Journal of Electrochemistry

Single particle impact electrochemistry (SPIEC) has grown rapidly in recent years and shown great promise in the analysis of nanoparticle properties as well as the detection of biomolecules including DNA, RNA, protein, enzyme, bacteria, virus, vesicles and others. This minireview summarizes recent advances in electroanalytical applications of SPIEC according to different analytical methods, i.e., direct electrolysis of nanoparticles or labeled nanoparticles, direct electrolysis of soft particles encapsulated redox molecule, indirect electrochemistry of particles, area and diffusion blocking, and changes in current magnitude and collision frequency.

Morphology And Detection Of Corrosion On Stainless Steel Reinforcement In Concrete, Julio J. Saire Yanez

USF Tampa Graduate Theses and Dissertations

Stainless steel (SS) has emerged as an alternative corrosion-resistant reinforcement in concrete instead of the commonly used carbon steel (CS). The biggest advantage of SS is that it takes more time for corrosion to initiate than for CS. An additional benefit from the use of SS in concrete may be derived from the period after the corrosion started until the concrete structure reaches a limit state. This period is called corrosion propagation stage (CPS) and it has been hardly studied in SS reinforced structures. The duration of this period could be related, among other factors, to the morphology of corrosion …

Electrochemical Upgrading Of Bio-Oil: A Proof-Of-Principle Investigation, Mehmet Pala, Kun Guo, Wolter Prins, Frederik Ronsse, Korneel Rabaey, Antonin Prévoteau

Pyroliq 2019: Pyrolysis and Liquefaction of Biomass and Wastes

Fast pyrolysis is an advanced thermochemical conversion technology developed to produce bio-oil from biomass. With lignocellulosic biomass, high product yields (65-75 wt.%) can be attained. Yet, certain unfavorable characteristics of bio-oil impede its utilization prospects. High water content, high oxygen content, together with instability and acidity are the recognized adverse features of bio-oil. Tackling these issues is possible by reducing the oxygen content and/or steering the oxygen functionality of bio-oils.

Electrochemical hydrogenation (ECH) is a recently proposed approach targeting the reduction of the reactive compounds in bio-oil (aldehydes, ketones etc.) to their corresponding alcohols, diols [1]. In this attractive approach, …

Surface Immobilization Of Terpyridine Compounds, Elizabeth Hallett

Chemical Engineering Undergraduate Honors Theses

The deoxydehydration (DODH) of polyols to alkenes is a promising method of producing high-value chemical feedstocks from biomass-derived materials. Current catalytic systems for DODH require the use of costly reducing agents that generate stoichiometric amounts of chemical waste. Immobilizing catalysts on electrode surfaces using chemical linking groups eliminates the need for sacrificial reductants. In this work, glassy carbon electrodes were modified with 4’-(3,4-dihydroxyphenyl)-2,2’:6’,2’’-terpyridine to investigate o-benzoquinone as a potential linking group for DODH, and possibly for other reactions. Previous studies involving electrodes modified with quinone-containing compounds have primarily been focused on catalyzing the oxidation of NADH; the nature or …

An Experimental And Numerical Investigation Of Flow Accelerated Flibe Corrosion, David B. Weitzel

Nuclear Engineering ETDs

Renewed interest in molten salt reactor technology has brought to light the need for a better understanding of FLiBe corrosion. To this end a flowing FLiBe corrosion test loop was designed to test the flow effects of FLiBe corrosion. The loop consists of a pump, melt tank, and stainless-steel tubing assembly that heats the molten salt to high temperatures and circulates it over test specimens. The experiment has been constructed and has completed initial shakedown testing.

To support the flowing FLiBe experiment, a numerical corrosion model that couples FLiBe electrochemistry, solid metal diffusion, and mass transport was implemented. The model …

Micro/Nanostructured Mnco2o4.5 Anodes With High Reversible Capacity And Excellent Rate Capability For Next Generation Lithium-Ion Batteries, Bin Wang, Shifeng Wang, Yuanyuan Tang, Chi-Wing Tsang, Jinchuan Dai, Michael K.H. Leung, Xiao-Ying Lu

Faculty of Science & Technology (THEi)

Lithium-ion batteries have already achieved great success in consumer electronics. However, the electrochemical characteristics of the existing electrodes have constrained their widespread applications in electric vehicles, which need technical demands of high energy density and fast charging. Thus, it is highly desirable to explore high-performance electrodes with high reversible capacity and excellent rate capability. In this study, micro/nanostructured MnCo2O4.5 anodes were synthesized by hydrothermal treatment with the presence of positively charged poly(diallyldimethylammonium chloride). Physicochemical property studies suggested that the as-prepared MnCo2O4.5 of 2–5 µm in diameter was mainly composed of numerous nanoneedles, which were further comprised of many inter-connected nanoparticles. …

Engineering Of Earth-Abundant Electrochemical Catalysts, Dylan D. Rodene

Theses and Dissertations

Alternative energy research into hydrogen production via water electrolysis addresses environmental and sustainability concerns associated with fossil fuel use. Renewable-powered electrolyzers are foreseen to produce hydrogen if energy and cost requirements are achieved. Electrocatalysts reduce the energy requirements of operating electrolyzers by lowering the reaction kinetics at the electrodes. Platinum group metals (PGMs) tend to be utilized as electrocatalysts but are not readily available and are expensive. Ni_1-xMo_x alloys, as low-cost and earth-abundant transition metal nanoparticles (NPs), are emerging as promising electrocatalyst candidates to replace expensive PGM catalysts in alkaline media. Pure-phase cubic and hexagonal Ni_{1-x …}

Novel Cathode Framework, Effective Electrolyte Modification, And Electrode Structural Modification Of High Performance Lithium Sulfur Batteries, Wenduo Zeng

Wayne State University Dissertations

Firstly, TiN nanotube arrays have been investigated as an effective skeleton in the cathode of lithium-sulfur batteries. A series of TiN nanotubes with various diameter and length have been synthesized and tested. Moreover, graphene nanoplatelets have been utilized as a structural anchor to support the TiN nanotubes, and the synergetic effect of composite material and its enhancement on Li-S battery electrochemical performance and cycling stability have been studied. Secondly, the improvement of electrode structural design has been evaluated for their effectiveness by using an in-situ characterization method with other electrochemical characterization. Lastly, the facile method of using transition metal cations …

Chronoamperometry Analysis Of Sweat Sensor Technology, Evan Fritz

Williams Honors College, Honors Research Projects

Due to the demand for in-situ electrolyte sodium sensors, prototype sensors have been produced to create a product for athletes and marathoners to monitor hydration levels. These senors address a desire in the marketplace for athletic monitoring for overall athlete wellness and performance. Sweat sensor samples were created using Multi-walled Carbon Nanotubes functionalized on a Nylon-6 fiber mat using cyclo-oligomeric Calixarene. This production process produces sensors capable of detecting sodium ion concentration present in human sweat in presence of an electric current. Chronoamperometry analysis is used in this manner to determine the functionality of the sensors. Much of the research …

Electrochemical Separation Of Multivalent Species On A Liquid Bismuth Cathode In Licl-Kcl Eutectic For Used Nuclear Fuel Reprocessing, Michael Woods

Theses and Dissertations

The presence of group I/II fission products (Cs-137, Sr-90, and Ba-137) within molten salt nuclear processes degrades operational efficiencies by contributing to increased radiation levels in the case of material handling processes or to loss of criticality in the case of a reactor. While methods such as zone freezing and ion exchange have been proven for the separation of these fission products in LiCl-KCl salts, they require extra equipment and processing steps. Addition of a liquid metal electrode to molten salt media, such as the electrorefiner of a pyroprocessing scheme or the salt cleaning stage of a molten salt fast …