Nanoscience and Nanotechnology Commons^™

The Development Of An Advanced Biorefinery To Produce Cellulosic Sugars And Bionanomaterials, Carlaile Fernanda De Oliveira Nogueira

Electronic Theses and Dissertations

Market trends show growing interest in cellulose nanomaterials due to their low environmental impact. However, current nanocellulose isolation technologies face technoeconomic and life cycle limitations. Previous research has shown that enzymatic treatments effectively reduce the energy input for mechanical nanocellulose isolation. Simultaneously, there is potential to improve the viability of cellulosic ethanol facilities by coproducing nanocelluloses as high-value product obtained from agricultural feedstock. Here, our goal was to study the mass balance of enzymatic-mechanical processes that coproduces cellulosic sugars and nanocelluloses, evaluating the technical feasibility of converting lignified and non-lignified materials.

First, we have determined a feasible 50:50 mass ratio …

From Waste To Energy: The Electrochemical Reduction Of Co2 Using Recycled Nanostructured Catalysts, Ibrahim Badawy

Theses and Dissertations

The reduction of carbon dioxide (CO₂RR) using electrochemistry is a promising solution for the burgeoning global energy crisis. The overall vision of its implementation relies on renewable energy sources to power the reaction creating carbon neutral products and effectively closing the carbon cycle. Research in this field has come a long way since its inception in the mid-1900s. However, there remain significant hurdles and important considerations to overcome in order to reach full commercialization. Most electrocatalysts tested for CO₂RR have been designed solely for maximum performance while ignoring the environmental consequences if such a material were …

Photocatalytic Degradation Of Organic Contaminants By Titania Particles Produced By Flame Spray Pyrolysis, Noah Babik

Theses and Dissertations

Advanced oxidation of organic pollutants with TiO2 photocatalysts is limited due to the wide bandgap of TiO2, 3.2 eV, which requires ultraviolet (UV) radiation. When nanosized TiO2 is modified by carbon doping, charge recombination is inhibited and the bandgap is narrowed, allowing for efficient photodegradation under visible light. Here, we propose a flame spray pyrolysis (FSP) technique to create TiO2. The facile process of FSP has been successful in preparing highly crystalline TiO2 nanoparticles. Using the same procedure to deposit TiO2 onto biochar, the photocatalyst was doped by the carbonaceous material. The morphology, crystalline and electronic structure of the FSP …

Computational Rational Design Of Electrocatalysts For Electrochemical Ammonia And Hydrogen Synthesis, Akash Jain

Doctoral Dissertations

The electrochemical hydrogen evolution reaction (HER) and nitrogen reduction reaction (NRR) offer fossil-fuel-free routes for hydrogen and ammonia synthesis, respectively. However, currently, both processes lack suitable electrocatalysts for practical applications. Thus, this dissertation focuses on the computational rational design of HER and NRR electrocatalysts. HER is most efficiently catalyzed by platinum (Pt), which is expensive. To reduce the catalyst cost, we investigate core-shell nanoparticles of inexpensive tungsten-carbide (WC) and Pt (WC@Pt). Using first-principles density functional theory (DFT) calculations, we compare the suitability of two WC phases, α-WC and β-WC as support materials for Pt overlayers. We dope WC with titanium …

Controlling The Emission Of Volatile Platinum Oxides To The Vapor Phase In Diesel Oxidation Catalysts, Arnab Ghosh

Nanoscience and Microsystems ETDs

Pt-based catalysts are used for the treatment of emissions from vehicles, particularly in Diesel oxidation catalysts (DOCs). Three-way catalysts are treated at temperatures ranging from 950℃-1050℃ while DOCs are aged at 800℃ for 50 hrs. At 800°C, Pt reacts with O₂ to form PtO₂ which has a high vapor pressure and can be transported through the vapor phase. These accelerated aging conditions lead to the formation of large Pt particles causing a loss of catalytic activity. In this thesis, we used model thin-film catalysts that made it possible to quantify the emission of Pt to the vapor phase …

Rational Design Of Highly Efficient Electrocatalysts Using Atomic Layer Deposition: From Nanoparticle To Single Atom, Junjie Li

Electronic Thesis and Dissertation Repository

Polymer electrolyte membrane fuel cells (PEMFCs) have been attracted significant attention due to their high energy efficiency. The electrocatalyst is one of the most important parts. However, state-of-the-art electrocatalysts suffer from several challenges, including 1) low stability under harsh working conditions; 2) low atomic utilization efficiency, especially for noble metals. This thesis, therefore, focuses on the design of highly efficient and stable electrocatalysts from nanoparticles down to single atoms using atomic layer deposition (ALD) and further understand the insight mechanisms.

Firstly, Pt nanoparticles are selectively deposited on the TiO₂ modified N-doped carbon nanotubes. The strong metal-support interactions between Pt …

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, …

Manufacturing Of Carbon-Based Hybrid Nanocomposites With Engineered Functionalities Via Laser Ablation Synthesis In Solution (Lasis) Techniques, Erick Leonardo Ribeiro

Doctoral Dissertations

Carbon-based composite materials have long been fabricated and extensively used in our daily lives. In the past decades, with rapid development of nanotechnology, these class of material have gained even more attention owing to their outstanding properties which directly results in their prospects to revolutionize technological development in many fields, ranging from medicine to electronics. Nevertheless, for certain applications, including electrochemical energy storage/conversion devices, the chemically inert nature of these materials creates obstacles and thus requires their coupling with other active species. This thesis explores the use of Laser Ablation Synthesis in Solution (LASiS) in tailoring promising strategies and pathways …

The Artificial Leaf: An Investigation Into The Sociotechnical Integration Of New Solar Energy Innovations, Alexandra K. Treml, Jamie M. Mears

Senior Honors Projects, 2020-current

Increasing global demand, combined with the volatility of fossil fuels, has called for a large-scale increase in renewable energy production. Photovoltaics hold significant potential, but by nature, solar energy is intermittent and lacks dispatchability. Researchers around the world are working to create innovative solutions that utilize semiconductors found in solar cell technologies in new ways. This project harnesses photoelectrochemical water-splitting, which uses light energy to dissociate water molecules into hydrogen and oxygen. When the water-splitting device is submerged in saltwater and illuminated by sunlight, oxygen and hydrogen gas are produced on opposite surfaces, and can be either released or stored …

Engineered Nanoparticles For Site-Specific Bioorthogonal Catalysis: Imaging And Therapy, Riddha Das

Doctoral Dissertations

Bioorthogonal catalysis offers a strategy for chemical transformations complementary to bioprocesses and has proven to be a powerful tool in biochemistry and medical sciences. Transition metal catalysts (TMCs) have emerged as a powerful tool to execute selective chemical transformations, however, lack of biocompatibility and stability limits their use in biological applications. Incorporation of TMCs into nanoparticle monolayers provides a versatile strategy for the generation of bioorthogonal nanocatalysts known as “nanozymes”. We have fabricated a family of nanozymes using gold nanoparticles (AuNPs) as scaffolds featuring diverse chemical functional groups for controlled localization of nanozymes in biological environments, providing unique strategies for …

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 …

Electrocatalysts With High Activity And Stability For Polymer Electrolyte Membrane Fuel Cells, Zhongxin Song

Electronic Thesis and Dissertation Repository

In addressing the activity and durability challenges facing electrocatalysts in polymer electrolyte membrane fuel cells (PEMFCs), atomic layer deposition (ALD) is emerging as a powerful technique for deposition of noble metals and transition metal oxides due to its exclusive advantages over other methods. The primary advantages of ALD are derived from the sequential, self-saturating, gas-surface reactions, and angstrom level control that take place during the deposition process. Therefore, ALD possesses the advantage in precisely control the particle size and uniform distribution on the substrate. By forming chemical bonds between the initial layer of ALD precursor and support atoms during the …

Degradation Of Orange G Through Persulfate Activated Nanoscale Zerovalent Iron Composites And Boron-Doped Diamond Electrodes, Suzana Ivandic

Chemical Engineering Undergraduate Honors Theses

Properly treated wastewater is necessary for water reuse and to avoid unnecessary impacts on the environment. The poultry industry utilizes large amounts of water for poultry processing. The need for innovative ways to treat organic contaminants in the poultry wastewater industry is especially necessary due to increased poultry consumption. The U.S. Department of Agriculture projected Americans would consume approximately 92 pounds of chicken per person in 2017.¹ Dissolved air flotation (DAF) is currently used in poultry wastewater treatment, but DAF does not remove organic contaminants efficiently per effluent standards. Implementation of processes that degrade contaminants directly would benefit the …

Surface Area And Electrocatalytic Properties Of Feni Nanoparticles For The Oxygen Evolution Reaction (Oer), James Burrow

Chemical Engineering Undergraduate Honors Theses

Iron-nickel bimetallic electrocatalysts have recently emerged as some of the best candidates for the oxygen evolution reaction (OER) in alkaline electrolyte. Understanding the effects of composition and morphology of iron-nickel nanoparticles is crucial for optimization and enhanced electrocatalyst performance. Both physical surface area and electrochemical surface area (ECSA) are functions of morphology. In this study, four different iron-nickel nanoparticle catalysts were synthesized. The catalysts were varied based on morphology (alloy versus core-shell) and composition (low, medium, and high stabilizer concentration). Brunauer-Emmett-Teller (BET) surface area analysis was conducted on three of the synthesized iron-nickel nanoparticles using a physisorption analyzer while electrochemical …

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 …

Graphene As A Solid-State Ligand For Palladium Catalyzed Cross-Coupling Reactions, Yuan Yang

Theses and Dissertations

Palladium-catalyzed carbon-carbon cross-coupling reactions have emerged a broadly useful, selective and widely applicable method to synthesize pharmaceutical active ingredients. As currently practiced in the pharmaceutical industry, homogeneous Pd catalysts are typically used in cross-coupling reactions. The rational development of heterogeneous catalysts for cross-coupling reactions is critical for overcoming the major drawbacks of homogeneous catalysis including difficulties in the separation, purification, and quality control process in drug production. In order to apply heterogeneous catalysis to flow reactors that may overcome this limitation, the catalyst must be strongly bound to a support, highly stable with respect to leaching, and highly active. While …

Surface And Structural Modification Of Carbon Electrodes For Electroanalysis And Electrochemical Conversion, Yan Zhang

Theses and Dissertations--Chemistry

Electrocatalysis is key to both sensitive electrochemical sensing and efficient electrochemical energy conversion. Despite high catalytic activity, traditional metal catalysts have poor stability, low selectivity, and high cost. Metal-free, carbon-based materials are emerging as alternatives to metal-based catalysts because of their attractive features including natural abundance, environmental friendliness, high electrical conductivity, and large surface area. Altering surface functionalities and heteroatom doping are effective ways to promote catalytic performance of carbon-based catalysts. The first chapter of this dissertation focuses on developing electrode modification methods for electrochemical sensing of biomolecules. After electrochemical pretreatment, glassy carbon demonstrates impressive figures-of-merit in detecting small, redox-active …

Fabrication And Modification Of Titania Nanotube Arrays For Harvesting Solar Energy And Drug Delivery Applications, Ahmed El Ruby Abdel Rahman Mohamed

Electronic Thesis and Dissertation Repository

The fast diminishing of fossil fuels in the near future, as well as the global warming caused by increasing greenhouse gases have motivated the urgent quest to develop advanced materials as cost-effective photoanodes for solar light harvesting and many other photocatalytic applications. Recently, titania nanotube arrays (TNTAs) fabricated by anodization process has attracted great interest due to their excellent properties such as: high surface area, vertically oriented, highly organized, one-dimensional, nanotubular structure, photoactivity, chemical stability and biocompatibility. This unique combination of excellent properties makes TNTAs an excellent photoanode for solar light harvesting. However, the relatively wide band gap energy of …

Ion Size Effects On The Properties Of Charge Regulating Electric Double Layers, Divya Jyoti Prakash

Nanoscience and Microsystems ETDs

The behavior of charged interfaces formed in various systems like colloidal solution, fuel cells, battery, electro-deposition, catalysis is governed by the properties of electrical double layer(EDL). Civilized model with charge regulation boundary condition determined by thermodynamic equilibrium at the interface has been used to model electrical double layer and shows that size of the solvent plays a critical role in characterizing the properties of EDL using classical density functional theory.This thesis investigates the impact of ion size in electrolyte solutions on the electrical double layer formed at the interface using a similar model. It is found that ion size greatly …

Graphite And Graphene-Oxide Based Pgm-Free Model Catalysts For The Oxygen Reduction Reaction, Joseph Henry Dumont

Nanoscience and Microsystems ETDs

The world currently relies heavily on fossil fuels such as coal, oil, and natural gas for its energy. Fossil fuels are non-renewable, that is, they draw on finite resources that will eventually dwindle, becoming too expensive or too environmentally damaging to retrieve. One alternative source of energy are fuel cells, electrochemical devices that convert chemical energy to cleanly and efficiently produce electricity. They can be used in a wide range of applications, including transportation, stationary, portable and emergency power sources. Their development has been slowed by the high cost of PGM electrocatalysts needed at both electrodes as well as sluggish …

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 …

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 …

Doped Tio2 Nanowires For Applications In Dye Sensitized Solar Cells And Sacrifical Hydrogen Production, Qasem Alsharari

Electronic Thesis and Dissertation Repository

This thesis explores the synthesis of metal oxide 1-D nanowires using a sol-gel method in supercritical carbon dioxide (sc-CO₂), as an environmental friendly enabling solvent. Porous nanowires were synthesized and their performance was tested in dye sensitized solar cell and sacrifical hydrogen production. Titanium isopropoxide (TIP) was used as a precursor for titania synthesis while copper, bismuth and indium were examined as dopants, respectively. The sol-gel reactions were catalyzed by acetic acid in CO₂ at a temperature of 60 °C and pressure of 5000 psi. It was observed that acetic acid/monomer ratio > 4 produced nanowires while a …

Designed Synthesis Of Nanoporous Organic Polymers For Selective Gas Uptake And Catalytic Applications, Pezhman Arab

Theses and Dissertations

Design and synthesis of porous organic polymers have attracted considerable attentions during the past decade due to their wide range of applications in gas storage, gas separation, energy conversion, and catalysis. Porous organic polymers can be pre-synthetically and post-synthetically functionalized with a wide variety of functionalities for desirable applications. Along these pursuits, we introduced new synthetic strategies for preparation of porous organic polymers for selective CO₂ capture.

Porous azo-linked polymers (ALPs) were synthesized by an oxidative reaction of amine-based monomers using copper(I) as a catalyst which leads to azo-linkage formation. ALPs exhibit high surface areas of up to 1200 …

Structure And Energetics Of Nanoparticles And Ionomer Films In Fuel Cell Catalyst Layers, Qianping He

Doctoral Dissertations

Improving the durability and utilization efficiency of the platinum-on-carbon (Pt/C) catalyst is of vital importance to the commercialization of the polymer electrolyte membrane fuel cell (PEMFC). This body of work provides molecular level insights to aid the fulfillment of this goal. Chapter 1 describes the use of molecular dynamics (MD) simulation in an effort to understand the Pt/C degradation issue from the nano-adhesion point of view. The roles of catalyst nanoparticle size, shape, Pt/C surface oxidation and the extent of ionomer film hydration are investigated to study their effects on nano-particle adhesion. It is found that the adhesion force strengthens …

Refractive Index Chemical Sensing With Noble Metal Nanoparticles, Phillip Blake

Graduate Theses and Dissertations

Chemical sensing is a key component in modern society, especially in engineering applications. Because of their widespread impact, improvements to chemical sensors are a significant area of research. One class of sensors, plasmonic sensors, is being heavily researched because of their ability to detect low levels of analyte in near real time without destroying the analyte. This work studies a new class of plasmonic sensor that utilizes diffractive coupling to improve sensor performance. Specifically, this work outlines the first study of diffractive coupling sensors with typical nanoparticle shapes. Sensitivity of this new class of sensor is directly compared to typical …