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Top-Down And Bottom-Up Fabrication Of Key Components In Miniature Energy Storage Devices, Wenhao Li Jan 2019

Top-Down And Bottom-Up Fabrication Of Key Components In Miniature Energy Storage Devices, Wenhao Li

Doctoral Dissertations

The advent of miniature electronic devices demands power sources of commensurate form factors. This spurs the research of micro energy storage devices, e.g., 3D microbatteries. A 3D microbattery contains nonplanar microelectrodes with high aspect ratio and high surface area, separated by a nanoscale electrolyte. The device takes up a total volume as small as 10 mm3, allowing it to serve on a chip and to provide power in-situ. The marriage of nanotechnology and electrochemical energy storage makes microbattery research a fascinating field with both scientific excitement and application prospect. However, successful fabrication of well-functioned key components and the ...


Nanoparticle Catalytic Enhancement Of Carbon Dioxide Reforming Of Methane For Hydrogen Production, Nicholas Groden Nov 2018

Nanoparticle Catalytic Enhancement Of Carbon Dioxide Reforming Of Methane For Hydrogen Production, Nicholas Groden

Doctoral Dissertations

The U.S. produces 5559.6 million metric tons of carbon dioxide annually, of which 21% is produced by industrial processes. Steam reforming, an industrial process that accounts for 95% of all hydrogen production in industry, produces 134.5 million metric tons of carbon dioxide or around 11% of the total carbon dioxide produced by industry. This carbon dioxide is then either emitted or goes through a sequestration process that accounts for 75% of the plant's operational costs. An alternative reaction to steam reforming is dry reforming, which utilizes carbon dioxide rather than emitting it and can be used ...


Transport Of Water And Ions Through Single-Walled Armchair Carbon Nanotubes: A Molecular Dynamics Study, Michelle Patricia Aranha Dec 2017

Transport Of Water And Ions Through Single-Walled Armchair Carbon Nanotubes: A Molecular Dynamics Study, Michelle Patricia Aranha

Doctoral Dissertations

The narrow hydrophobic interior of a carbon nanotube (CNT) poses a barrier to the transport of water and ions, and yet, unexpectedly, numerous experimental and simulation studies have confirmed fast water transport rates comparable to those seen in biological aquaporin channels. These outstanding features of high water permeability and high solute rejection of even dissolved ions that would typically require a lot of energy for separation in commercial processes makes carbon nanotubes an exciting candidate for desalination membranes. Extending ion exclusion beyond simple mechanical sieving by the inclusion of electrostatics via added functionality to the nanotube bears promise to not ...


Synthesis, Characterization, And Activity Of Co/Fe Alumina/Silica Supported Ft Catalysts And The Study Of Promoter Effect Of Ruthenium, Sunday Azubike Esumike Jan 2017

Synthesis, Characterization, And Activity Of Co/Fe Alumina/Silica Supported Ft Catalysts And The Study Of Promoter Effect Of Ruthenium, Sunday Azubike Esumike

Doctoral Dissertations

The alumina and hybrid alumina-silica FT catalyst were prepared by one-step solgel/oil-drop methods using metal-nitrate-solutions (method-I), and nanoparticle-metaloxides (method-2). The nanoparticle-metal-oxides did not participate in solubility equilibria in contrast to metal nitrate in method-1 causing no metal ion seepage; therefore, method-2 yields higher XRF metal loading efficiency than method-1. The thermal analysis confirmed that the metal loading by method-1 and method-2 involved two different pathways. Method-1 involves solubility equilibria in the conversion of metal-nitrate to metal- hydroxide and finally to metal-oxide, while in method-2 nanoparticle-metal-oxide remained intact during sol-gel-oil-drop and calcination steps.

The alumina supported catalysts were dominated by ...


The Rheology And Roll-To-Roll Processing Of Shear-Thickening Particle Dispersions, Sunilkumar Khandavalli Jan 2017

The Rheology And Roll-To-Roll Processing Of Shear-Thickening Particle Dispersions, Sunilkumar Khandavalli

Doctoral Dissertations

Particle dispersions are ubiquitous in our daily lives ranging from food and pharmaceutical products to inks. There has been great interest in the recent years in formulation of functional inks to fabricate myriad flexible electronic devices through high-throughput roll-to-roll technologies. The formulations often contain several functional additives or rheological modifiers that can affect the microstructure, rheology and processing. Understanding the rheology of formulations is important for tuning the formulation for optimal processing. This thesis presents investigations on the rheology of particle dispersions and their impact on roll-to-roll technologies.

Shear-thickening behavior is common in particle dispersions, particularly, concentrated particulate inks. We ...


Modeling Of Nanoscale Transport In Mesoporous Membranes, Ashutosh Rathi Jan 2017

Modeling Of Nanoscale Transport In Mesoporous Membranes, Ashutosh Rathi

Doctoral Dissertations

Mesoporous membranes with pore sizes in the range 2-50 nm provide an energy efficient alternative for separation of mixtures such as CO2 from stack effluents and volatile organic compounds (VOC) from air. Transport mechanisms such as capillary condensation, Knudsen diffusion and surface adsorption help in enrichment of a more condensable component based on the bulk mixture thermodynamics, surface chemistry and geometry of the mesopores. Despite the progress in synthesis techniques, design of better mesoporous materials for targeted separations is still a challenge due to the absence of clear design rules. Modeling techniques can be used to quantify the relevant ...


Immobilization Of Cellulase For Large Scale Reactors To Reduce Cellulosic Ethanol Cost, Dezhi Zhang Apr 2016

Immobilization Of Cellulase For Large Scale Reactors To Reduce Cellulosic Ethanol Cost, Dezhi Zhang

Doctoral Dissertations

Cellulosic ethanol is an alternative renewable energy source. Cellulase used in the production of cellulosic ethanol is very expensive. The difficulty in separating cellulase from the cellulose solution after the hydrolysis process limits the reusability of the cellulase, which highly precludes the scales of this application because of the high cost of the enzyme. Immobilization of cellulase provides a promising approach to allow the enzyme to be recycled, thus reducing the production cost. This research focused on immobilizing cellulase for reuse to reduce the cellulosic ethanol cost.

Four immobilization techniques were explored for the immobilization of cellulase on four different ...


Manufacturing Polyacrylonitrile Nanowires And Nanofibers For Sensing And Energy Storage Applications, Juan Chen Apr 2016

Manufacturing Polyacrylonitrile Nanowires And Nanofibers For Sensing And Energy Storage Applications, Juan Chen

Doctoral Dissertations

A novel flow guided assembly approach is presented to well align and accurately position nanowire arrays in pre-defined locations with high throughput and large scale manufacturing capability. In this approach, polyacrylonitrile (PAN)/N, N-dimethylformamide (DMF) solution is first filled in an array of microfluidic channels. Then a gas flow is introduced to blow out most solutions while pushing a little leftover against the channel wall to assemble into polymer nanowires. In this way, highly-ordered nanowires are conveniently aligned in the flow direction and patterned along both sides of the microchannels. In this study, we demonstrated this flow-guided assembly process by ...


Kinetics And Dynamics Of Electrophoretic Translocation Of Polyelectrolytes Through Nanopores, Harshwardhan Katkar Jan 2016

Kinetics And Dynamics Of Electrophoretic Translocation Of Polyelectrolytes Through Nanopores, Harshwardhan Katkar

Doctoral Dissertations

The idea of sequencing a DNA based on single-file translocation of the DNA through nanopores under the action of an electric field has received much attention over the past two decades due to the societal need for low cost and high-throughput sequencing. However, due to the high speed of translocation, interrogating individual bases with an acceptable signal to noise ratio as they traverse the pore has been a major problem. Experimental facts on this phenomenon are rich and the associated phenomenology is yet to be fully understood. This thesis focuses on understanding the underlying principles of polymer translocation, with an ...


Label-Free And Aptamer-Based Surface Enhanced Raman Spectroscopy For Detection Of Food Contaminants, Shintaro Pang Jan 2016

Label-Free And Aptamer-Based Surface Enhanced Raman Spectroscopy For Detection Of Food Contaminants, Shintaro Pang

Doctoral Dissertations

The development of analytical methods to detect food contaminants is a critical step for improving food safety. Surface enhanced Raman spectroscopy (SERS) is an emerging detection technology that has the potential to rapidly, accurately and sensitively detect a wide variety of food contaminants. However, SERS detection becomes a challenge in real complex matrix, such as food, since non-specific matrix signals have the potential to drown out target associated Raman peaks. In this dissertation, we focused on the development and application of label-free, aptamer-based SERS in order to improve the accuracy and specificity of target contaminant detection in food. To accomplish ...


Solution And Surface Properties Of Architecturally- And Compositionally-Complex Block Copolymers And Their Binary Mixtures, Jesse Lawrence Davis Dec 2015

Solution And Surface Properties Of Architecturally- And Compositionally-Complex Block Copolymers And Their Binary Mixtures, Jesse Lawrence Davis

Doctoral Dissertations

The spontaneous generation of complex structures from polymeric building blocks provides a simple yet effective route to create useful soft matter structures having potential application in a variety of nanotechnologies. The topology, chemical structure, block composition, and sequence of the constituent building blocks of polymers are tunable through synthetic chemistry. This tunability offers attractive opportunities to generate complex, yet well-defined structures with control over the geometry, packing symmetry, and microdomain structure. This thesis work involves the study of the self-assembly behaviors of architecturally complex amphiphilic block copolymers (ABCs). ABCs are composed of two or more chemically distinct blocks that are ...


Functional Clay Nanotubes And Composites, Yafei Zhao Apr 2015

Functional Clay Nanotubes And Composites, Yafei Zhao

Doctoral Dissertations

Tubular nanomaterials and their composites have been extensively studied in recent years in the fields of physics, chemistry, biology, and biomedicine. Carbon nanotube is the most commonly studied tubular nanomaterial; however, toxicity and high cost make it less attractive in industry and thus restricts its applications. Halloysite nanotubes, which are available in abundance in the United States as well as in other countries around the world, is a low-cost, unique and versatile aluminosilicate mineral with a chemical formula of Al4Si4O10(OH)8·nH2O. Basically, the halloysite tube diameter is around 50 nm and the length varies with different locations ranging ...


Functional Nanostructures From Nanoparticle Building Blocks, Jimmy Lawrence Jan 2015

Functional Nanostructures From Nanoparticle Building Blocks, Jimmy Lawrence

Doctoral Dissertations

Advances in the synthetic strategies of engineered nanomaterials, multifunctional molecules and polymers have opened pathways for the development of functional nanomaterials having unique optoelectronic, mechanical, and biological properties. By designing the chemistry of surface ligands, the organic interface of nanoparticles, one can further the versatility and utilization of engineered nanomaterials, opening pathways for breakthroughs in sensing, catalysis, and delivery using nanomaterials.

This thesis describes the synthesis and characterization of small molecule and polymer ligand functionalized inorganic nanoparticles (e.g., metal, semiconducting). Embedding specific chemical functionality into the ligand periphery of nanoparticles enables the resulting functional nanoparticles to react selectively with ...


Computational Study Of Sodium Magnesium Hydride For Hydrogen Storage Applications, Fernando Antonio Soto Valle Oct 2014

Computational Study Of Sodium Magnesium Hydride For Hydrogen Storage Applications, Fernando Antonio Soto Valle

Doctoral Dissertations

Hydrogen offers considerable potential benefits as an energy carrier. However, safe and convenient storage of hydrogen is one of the biggest challenges to be resolved in the near future. Sodium magnesium hydride (NaMgH 3) has attracted attention as a hydrogen storage material due to its light weight and high volumetric hydrogen density of 88 kg/m3. Despite the advantages, hydrogen release in this material occurs at approximately 670 K, which is well above the operable range for on-board hydrogen storage applications. In this regard, hydrogen release may be facilitated by substitution doping of transition-metals. This dissertation describes first-principles computational methods ...


Study And Development Of Sulfated Zirconia Based Proton Exchange Fuel Cell Membranes, Brittany Wilson Kemp Apr 2014

Study And Development Of Sulfated Zirconia Based Proton Exchange Fuel Cell Membranes, Brittany Wilson Kemp

Doctoral Dissertations

With the increasing consumption of energy, fuel cells are among the most promising alternatives to fossil fuels, provided some technical challenges are overcome. Proton exchange membrane fuel cells (PEMFCs) have been investigated and improvements have been made, but the problem with Nafion®, the main membrane for PEMFCs, has not been solved. Nafion® restricts the membranes from operating at higher temperatures, thus preventing them from working in small electronics. The problem is to develop a novel fuel cell membrane that performs comparably to Nafion® in PEMFCs.

The membranes were fabricated by applying sulfated zirconia, via template wetting, to porous alumina membranes ...


Adsorption And Diffusion Of Gases In Nano-Porous Materials, Nethika Sahani Suraweera Dec 2013

Adsorption And Diffusion Of Gases In Nano-Porous Materials, Nethika Sahani Suraweera

Doctoral Dissertations

In this work, a systematic computational study directed toward developing a molecular-level understanding of gas adsorption and diffusion characteristics in nano-porous materials is presented. Two different types of porous adsorbents were studied, one crystalline and the other amorphous. Physisorption and diffusion of hydrogen in ten iso-reticular metal-organic frameworks (IRMOFs) were investigated. A set of nine adsorbents taken from a class of novel, amorphous nano-porous materials composed of spherosilicate building blocks and isolated metal sites was also studied, with attention paid to the adsorptive and diffusive behavior of hydrogen, methane, carbon dioxide and their binary mixtures. Both classes of materials were ...


Structure And Energetics Of Nanoparticles And Ionomer Films In Fuel Cell Catalyst Layers, Qianping He Dec 2013

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 ...


Multi-Scale Characterization Of Nanostructured Sodium Aluminum Hydride, Shathabish Narasegowda Jan 2013

Multi-Scale Characterization Of Nanostructured Sodium Aluminum Hydride, Shathabish Narasegowda

Doctoral Dissertations

Complex metal hydrides are the most promising candidate materials for onboard hydrogen storage. The practicality of this class of materials is counter-poised on three critical attributes: reversible hydrogen storage capacity, high hydrogen uptake/release kinetics, and favorable hydrogen uptake/release thermodynamics. While a majority of modern metallic hydrides that are being considered are those that meet the criteria of high theoretical storage capacity, the challenges lie in addressing poor kinetics, thermodynamics, and reversibility. One emerging strategy to resolve these issues is via nanostructuring or nano-confinement of complex hydrides. By down-sizing and scaffolding them to retain their nano-dimensions, these materials are ...


Role Of Ammonia In The Activiation Of Methanol Dehydrogenase/Cytochrome C(L) Enzyme, Ancy Kunjumon Oct 2011

Role Of Ammonia In The Activiation Of Methanol Dehydrogenase/Cytochrome C(L) Enzyme, Ancy Kunjumon

Doctoral Dissertations

Recent advancement in enzyme catalysis has opened ways to design efficient biocatalysts, bio-sensors and bio-fuel cells. An in-depth knowledge about the mechanism of the reaction taking place within the enzymes is of great importance to achieve these goals. In this dissertation, various computation methods are applied to investigate the mechanism behind enzyme catalysis in the presence of compounds called activators.

Methanol dehydrogenase (MDH) is a well-known bio-catalyst that can oxidize excess of methanol from the environment to formaldehyde. The enzyme works well within the bacterial environment, but under in vitro, it loses activity. Ammonia is used as an activator to ...


Halloysite Clay Nanotubes For Controlled Delivery Of Chemically Active Agents, Elshard Abdullayev Oct 2010

Halloysite Clay Nanotubes For Controlled Delivery Of Chemically Active Agents, Elshard Abdullayev

Doctoral Dissertations

In this work we explored the capabilities of halloysite nanotubes as capsules for encapsulation and controlled delivery of the chemically and biologically active substances. Halloysite is a two-layered aluminosilicate which has a predominantly hollow tubular structure in the submicron range and is chemically similar to kaolinite [1, 2].

In the first section of this work, we analyzed the structure of the halloysite nanotubes as well as its capability to encapsulate and deliver biologically and chemically active agents, similarities and differences between release characteristics of different agents and how these differences relate with their chemical structure. Models were used to describe ...


Molecular Simulations Of Adsorption And Diffusion In Metal-Organic Frameworks (Mofs), Ruichang Xiong May 2010

Molecular Simulations Of Adsorption And Diffusion In Metal-Organic Frameworks (Mofs), Ruichang Xiong

Doctoral Dissertations

Metal-organic frameworks (MOFs) are a new class of nanoporous materials that have received great interest since they were first synthesized in the late 1990s. Practical applications of MOFs are continuously being discovered as a better understanding of the properties of materials adsorbed within the nanopores of MOFs emerges. One such potential application is as a component of an explosive-sensing system. Another potential application is for hydrogen storage.

This work is focused on tailoring MOFs to adsorb/desorb the explosive, RDX. Classical grand canonical Monte Carlo (GCMC) and molecular dynamic (MD) simulations have been performed to calculate adsorption isotherms and self-diffusivities ...


Analysis Of Conjugated Polymer Nanotubules Formed By Template Wetting Nanofabrication, Steven D. Bearden Jr. Apr 2010

Analysis Of Conjugated Polymer Nanotubules Formed By Template Wetting Nanofabrication, Steven D. Bearden Jr.

Doctoral Dissertations

Semiconducting and optoelectric conjugated polymers have potential in micro and nano-electronic applications. Their widely tunable physical conformations and orientations make these polymers ideal material for engineering small scale devices. The polymers have been incorporated into several electronic devices including light-emitting diodes, solar cells, and field-effect transistors. Widespread adoption of these materials will not be a reality until the issues of poor device performance, short lifespans, and device degradation are resolved.

Nanostructures have been demonstrated to have improvements in molecular ordering and electronic transport. In the work presented here, tubular nanostructures of conjugated polymers fabricated by the template wetting nanofabrication process ...