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Description
Structural details of phosphonic acid functionalized nanomaterials and protic ionic liquids (PILs) were characterized using nuclear magnetic resonance (NMR) spectroscopy. It is well known that ligands play a critical role in the synthesis and properties of nanomaterials. Therefore, elucidating the details of ligand-surface and ligand-ligand interactions is crucial to

Structural details of phosphonic acid functionalized nanomaterials and protic ionic liquids (PILs) were characterized using nuclear magnetic resonance (NMR) spectroscopy. It is well known that ligands play a critical role in the synthesis and properties of nanomaterials. Therefore, elucidating the details of ligand-surface and ligand-ligand interactions is crucial to understanding nanomaterial systems more completely.

In an effort to further the understanding of ligand-surface interactions, a combination of multi-nuclear (1H, 29Si, 31P) and multi-dimensional solid-state NMR techniques were utilized to characterize the phosphonic acid functionalization of fumed silica nanoparticles using methyl phosphonic acid (MPA) and phenyl phosphonic acid (PPA). Quantitative 31P MAS solid-state NMR measurements indicate that ligands favor a monodentate binding mode. Furthermore, 1H-1H single quantum-double quantum (SQ-DQ) back-to-back (BABA) 2D NMR spectra of silica functionalized with MPA and PPA indicate that the MPA and PPA are within 4.2±0.2 Å on the surface of the nanomaterial.

The ligand capping of phosphonic acid (PA) functionalized CdSe/ZnS core-shell quantum dots (QDs) was investigated with a combination of ligand exchange, solution and solid-state 31P NMR spectroscopy. In order to quantify the ligand populations on the surface of the QDs, ligand exchange facilitated by PPA resulted in the displacement of the PAs, and allowed for quantification of the free ligands using 31P liquid state NMR.

In addition to characterizing nanomaterials, the ionicity and transport properties of a series of diethylmethylamine (DEMA) based protic ionic liquids (PILs) were characterized, principally utilizing NMR. Gas phase proton affinity was shown to be a better predictor for the extent of proton transfer, and in turn the ionicity of the PIL, than using ∆pKa. Furthermore, pulsed field gradient (PFG) NMR was used to determine that the exchangeable proton diffuses with the cation or the anion based on the strength of the acid used to generate the PILs.
ContributorsDavidowski, Stephen (Author) / Yarger, Jeffery L. (Thesis advisor) / Holland, Gregory P (Thesis advisor) / Angell, Charles A. (Committee member) / Buttry, Daniel A. (Committee member) / Arizona State University (Publisher)
Created2015
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Description
A meta-analysis was conducted to compare the total amount of ionic liquid (IL) literature (n = 39,036) to the body of publications dealing with IL toxicity (n = 213), with the goal of establishing the state of knowledge and existing information gaps. Publications on IL toxicity were collected from the

A meta-analysis was conducted to compare the total amount of ionic liquid (IL) literature (n = 39,036) to the body of publications dealing with IL toxicity (n = 213), with the goal of establishing the state of knowledge and existing information gaps. Publications on IL toxicity were collected from the SciFinder database and sorted by cation and model organism studied. Studies focusing on pharmacokinetics and drug development were excluded, as were structure-activity relationship methods of data collection. Total publishing activity was used as a measure to gauge research and industrial usage of ILs as well as the knowledge base of toxicology. Five of the most commonly studied IL cations were identified and used to establish a relationship between toxicity data and potential of commercial use: imidazolium, ammonium, phosphonium, pyridinium, and pyrrolidinium. Toxicology publications for all IL cations represented 1.2% ± 0.62% of the total publishing activity; compared with other industrial chemicals, these numbers indicate that there is still a paucity of studies on the adverse effects of this class of chemicals. In vitro models and marine bacteria were the most frequently studied biological systems, contributing 18% and 15%, respectively, to the total body of IL toxicity studies. Whole animal studies (n = 87) comprised 41% of IL toxicity studies, with a subset of in vivo mammalian models consisting of 8%. Human toxicology data were found to be limited to in vitro analyses, indicating substantial knowledge gaps. Risks from long-term and chronic low-level exposure to ILs have not been established yet for any model organisms, reemphasizing the need for filling crucial knowledge gaps concerning human health effects and the environmental safety of ILs. Adding to the existing knowledge of the molecular toxicity characteristics of ILs can help inform the design of greener, less toxic and more benign IL technologies.
ContributorsHeckenbach, Mary (Co-author) / Halden, Rolf (Co-author, Thesis director) / Jehn, Megan (Committee member) / Barrett, The Honors College (Contributor) / School of Life Sciences (Contributor)
Created2015-05
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Description
Iodide-based ionic liquids have been widely employed as sources of iodide in electrolytes for applications utilizing the triiodide/iodide redox couple. While adding a low-viscosity solvent such as water to ionic liquids can greatly enhance their usefulness, mixtures of highly viscous iodide-containing ILs with water have never been studied. Thus, this

Iodide-based ionic liquids have been widely employed as sources of iodide in electrolytes for applications utilizing the triiodide/iodide redox couple. While adding a low-viscosity solvent such as water to ionic liquids can greatly enhance their usefulness, mixtures of highly viscous iodide-containing ILs with water have never been studied. Thus, this paper investigates, for the first time, mixtures of water and the ionic liquid 1-butyl-3-methylimidazolium iodide ([BMIM][I]) through a combined experimental and molecular dynamics study. The density, melting point, viscosity and conductivity of these mixtures were measured experimentally. The composition region below 50% water by mole was found to be dramatically different from the region above 50% water, with trends in density and melting point differing before and after that point. Water was found to have a profound effect on viscosity and conductivity of the IL, and the effect of hydrogen bonding was discussed. Molecular dynamics simulations representing the same mixture compositions were performed. Molecular ordering was observed, as were changes in this ordering corresponding to water content. Molecular ordering was related to the experimentally measured mixture properties, providing a possible explanation for the two distinct composition regions identified by experiment.
ContributorsNgan, Miranda L (Author) / Dai, Lenore (Thesis director) / Nofen, Elizabeth (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2015-05
ContributorsEvans, Bartlett R. (Conductor) / Schildkret, David (Conductor) / Glenn, Erica (Conductor) / Concert Choir (Performer) / Chamber Singers (Performer) / ASU Library. Music Library (Publisher)
Created2018-03-16
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Description
The field of Ionic Liquid (IL) research has received considerable attention during the past decade. Unique physicochemical properties of these low melting salts have made them very promising for applications in a many areas of science and technology such as electrolyte research, green chemistry and electrodeposition. One of the most

The field of Ionic Liquid (IL) research has received considerable attention during the past decade. Unique physicochemical properties of these low melting salts have made them very promising for applications in a many areas of science and technology such as electrolyte research, green chemistry and electrodeposition. One of the most important parameters dictating their physicochemical behavior is the basicity of their anion. Using four sets of Protic Ionic Liquids (PILs) and spectroscopic characterization of them, a qualitative order for anion basicity of ILs is obtained.

Protic Ionic Liquids are made by proton transfer form a Brønsted acid to a base. The extent of this transfer is determined by the free energy change of the proton transfer process. For the cases with large enough free energy change during the process, the result is a fully ionic material whereas if the proton transfer is not complete, a mixture of ions, neutral molecules and aggregates is resulted. NMR and IR spectroscopies along with electrochemical and mechanical characterization of four sets of PILs are used to study the degree of ionicity.
ContributorsHasani, Mohammad (Author) / Angell, C. Austen (Thesis advisor) / Yarger, Jeffrey L (Committee member) / Gould, Ian R (Committee member) / Arizona State University (Publisher)
Created2016
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Description
This investigation is divided into two portions linked together by the momentous reaches of electrochemistry science, principles influencing everyday phenomena as well as innovative research in the field of energy transformation. The first portion explores the strategies for flue gas carbon dioxide capture and release using electrochemical means. The main

This investigation is divided into two portions linked together by the momentous reaches of electrochemistry science, principles influencing everyday phenomena as well as innovative research in the field of energy transformation. The first portion explores the strategies for flue gas carbon dioxide capture and release using electrochemical means. The main focus is in the role thiolates play as reversible strong nucleophiles with the ability to capture CO2 and form thiocarbonates. Carbon dioxide in this form is transported and separated from thiocarbonate through electrochemical oxidation to complete the release portion of this catch-and-release approach. Two testing design systems play a fundamental role in achieving an efficient CO2 catch and release process and were purposely build and adapted for this work. A maximum faradaic efficiency of seventeen percent was attained in the first membrane tests whose analysis is presented in this work. An efficiency close to thirty percent was attained with the membrane cell in recent experiments but have not been included in this manuscript.

The second portion of this manuscript studies bulk stress evolution resulting from insertion/extraction of lithium in/from a lithium manganese oxide spinel cathode structure. A cantilever-based testing system uses a sophisticated, high resolution capacitive technique capable of measuring beam deflections of the cathode in the subnanometer scale. Tensile stresses of up to 1.2 MPa are reported during delithiation along with compressive stresses of 1.0 MPa during lithiation. An analysis of irreversible charge loss is attributed to surface passivation phenomena with its associated stresses of formation following patterns of tensile stress evolution.
ContributorsCastro De la Torre, Helme Atic (Author) / Friesen, Cody (Thesis advisor) / Buttry, Daniel (Committee member) / Bautista Martinez, Jose A (Committee member) / Arizona State University (Publisher)
Created2016
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Description
Ionic liquids (ILs), or low-temperature liquid salts, are a class of materials with unique and useful properties. Made up entirely of ions, ILs are remarkably tunable and diverse as cations and anions can be mixed and matched to yield desired properties. Because of this, IL/water systems range widely—from homogeneous mixtures

Ionic liquids (ILs), or low-temperature liquid salts, are a class of materials with unique and useful properties. Made up entirely of ions, ILs are remarkably tunable and diverse as cations and anions can be mixed and matched to yield desired properties. Because of this, IL/water systems range widely—from homogeneous mixtures to multiphasic systems featuring ionic liquid/liquid interfaces. Even more diversity is added when particles are introduced to these systems, as hard particles or soft-matter microgels interact with both ILs and water in complex ways. This work examines both miscible ionic liquid/water mixture and two-phase, immiscible ionic liquid/water systems. Extensive molecular dynamics (MD) simulations are utilized in conjunction with physical measurements to inform theoretical understanding of the nature of these systems, and this theoretical understanding is related to practical applications—in particular, the development of a low-temperature liquid electrolyte for use in molecular electronic transducer (MET) seismometers, and particle self-assembly and transport at ionic liquid/liquid interfaces such as those in Pickering emulsions.

The homogenous mixture of 1-butyl-3-methylimidazolium iodide and water is examined extensively through MD as well as physical characterization of properties. Molecular ordering within the liquid mixture is related to macroscopic properties. These mixtures are then used as the basis of an electrolyte with unusual characteristics, specifically a wide liquid temperature range with an extremely low lower bound combined with relatively low viscosity allowing excellent performance in the MET sensor. Electrolyte performance is further improved by the addition of fullerene nanoparticles, which dramatically increase device sensitivity. The reasons behind this effect are explored by testing the effect of graphene surface size and through MD simulations of fullerene and a silica nanoparticle (for contrast) in [BMIM][I]/water mixtures.

Immiscible ionic liquid/water systems are explored through MD studies of particles at IL/water interfaces. By increasing the concentration of hydrophobic nanoparticles at the IL/water interface, one study discovers the formation of a commingled IL/water/particle pseudo-phase, and relates this discovery to previously-observed unique behaviors of these interfaces, particularly spontaneous particle transport across the interface. The other study demonstrates that IL hydrophobicity can influence the deformation of thermo-responsive soft particles at the liquid/liquid interface.
ContributorsNickerson, Stella Day (Author) / Dai, Lenore L (Thesis advisor) / Yu, Hongyu (Committee member) / Lind, Mary Laura (Committee member) / Mu, Bin (Committee member) / Emady, Heather (Committee member) / Arizona State University (Publisher)
Created2016
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Description
Recently, a number of publications have suggested that ionic liquids (ILs) can absorb solid particles. This development may have implications in fields like oil sand processing, oil spill beach cleanup, and water treatment. In this Honors Thesis, computational investigation of this phenomenon is provided via molecular dynamics simulations. Two particle

Recently, a number of publications have suggested that ionic liquids (ILs) can absorb solid particles. This development may have implications in fields like oil sand processing, oil spill beach cleanup, and water treatment. In this Honors Thesis, computational investigation of this phenomenon is provided via molecular dynamics simulations. Two particle surface chemistries were investigated: (1) hydrocarbon-saturated and (2) silanol-saturated, representing hydrophobic and hydrophilic particles, respectively. Employing 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]-[PF6]) as a model IL, these nanoparticles were allowed to equilibrate at the IL/water and IL/hexane interfaces to observe the interfacial self-assembled structures. At the IL/water interface, the hydrocarbon-based nanoparticles were nearly completely absorbed by the IL, while the silica nanoparticles maintained equal volume in both phases. At the IL/hexane interface, the hydrocarbon nanoparticles maintained minimal interactions with the IL, whereas the silica nanoparticles were nearly completely absorbed by it. Studies of these two types of nanoparticles immersed in the bulk IL indicate that the surface chemistry has a great effect on the corresponding IL liquid structure. These effects include layering of the ions, hydrogen bonding, and irreversible absorption of some ions to the silica nanoparticle surface. These effects are quantified with respect to each nanoparticle. The results suggest that ILs likely exhibit this absorption capability because they can form solvation layers with reduced dynamics around the nanoparticles.
ContributorsMachas, Michael Stafford (Author) / Dai, Lenore (Thesis director) / Lind, Mary Laura (Committee member) / Frost, Denzil (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2013-05
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Description
The following thesis documents a two-fold approach to investigate challenges pertaining to water purification, first through a meta-analysis of ionic liquid toxicity, then through experimentation aimed at developing water pre-treatment membranes. Ionic liquids (ILs) are salts with low melting points, typically liquid at room temperature. Several extraordinary physical attributes, e.g.

The following thesis documents a two-fold approach to investigate challenges pertaining to water purification, first through a meta-analysis of ionic liquid toxicity, then through experimentation aimed at developing water pre-treatment membranes. Ionic liquids (ILs) are salts with low melting points, typically liquid at room temperature. Several extraordinary physical attributes, e.g. low viscosity, high conductivity, low to no vapor pressure, etc., and seemingly unlimited combinations available, have pushed IL research to the forefront of many research fronts. Concerns are raised as ionic liquids are rushed into commercial production without sufficient environmental regulation. Research has shown that the chemicals are in fact toxic, yet have developed a reputation for being “green” chemicals due to select physical attributes and applications. The meta-analysis discussed focuses on industry perception of ionic liquid toxicity through a patent review, and considers toxicity of ILs comparatively against other chemical families with well-established toxicity. The meta-analysis revealed that the total patent literature pertaining to ILs (n=3358) resulted in 112 patents that addressed the toxicity of ILs, and notably few (n=17) patents defined ILs as toxic, representing only 0.51% of the evaluated body of work on intellectual property claims. Additionally, toxicity of ionic liquids is comparable to that of other chemical families.
The objective of the experimentation was to explore the effect of crosslinker chain length on the morphology of nanofiber mats. Specifically, poly(vinyl alcohol (PVA) was electrospun into nanofiber mats and poly(ethylene) glycol bis(carboxylic acid) (PEG diacid) was used as the crosslinking agent. As-spun fibers had average fiber diameter of 70 ± 30 nm with an average pore size of 0.10 ± 0.16 μm^2. The fiber diameter for the mats crosslinked with the shorter PEG diacid (Mn = 250) increased to 110 ± 40 nm with an average pore size of 0.11 ± 0.04 μm^2. The mats crosslinked with the longer PEG diacid (Mn = 600) had fiber diameters of 180 ± 10 nm with an average pore size 0.01 ± 0.02 μm^2.
ContributorsRomero, Felicia Navidad (Author) / Green, Matthew D. (Thesis director) / Lind, Mary Laura (Committee member) / Long, Timothy E. (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
ContributorsOwen, Ken (Conductor) / McDevitt, Mandy L. M. (Performer) / Larson, Brook (Conductor) / Wang, Lin-Yu (Performer) / Jacobs, Todd (Performer) / Morehouse, Daniel (Performer) / Magers, Kristen (Performer) / DeGrow, Gary (Performer) / DeGrow, Richard (Performer) / Women's Chorus (Performer) / Sun Devil Singers (Performer) / ASU Library. Music Library (Publisher)
Created2004-03-24