Matching Items (4)
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- All Subjects: 2D materials
- All Subjects: Metal-organic frameworks
- Genre: Academic theses
- Creators: Green, Matthew
- Status: Published
Description
An urgent need for developing new chemical separations that address the capture of dilute impurities from fluid streams are needed. These separations include the capture of carbon dioxide from the atmosphere, impurities from drinking water, and toxins from blood streams. A challenge is presented when capturing these impurities because the energy cost for processing the bulk fluid stream to capture trace contaminants is too great using traditional thermal separations. The development of sorbents that may capture these contaminants passively has been emphasized in academic research for some time, producing many designer materials including metal-organic frameworks (MOFs) and polymeric resins. Scaffolds must be developed to effectively anchor these materials in a passing fluid stream. In this work, two design techniques are presented for anchoring these sorbents in electrospun fiber scaffolds.
The first technique involves imbedding sorbent particles inside the fibers: forming particle-embedded fibers. It is demonstrated that particles will spontaneously coat themselves in the fibers at dilute loadings, but at higher loadings some get trapped on the fiber surface. A mathematical model is used to show that when these particles are embedded, the polymeric coating provided by the fibers may be designed to increase the kinetic selectivity and/or stability of the embedded sorbents. Two proof-of-concept studies are performed to validate this model including the increased selectivity of carbon dioxide over nitrogen when the MOF ZIF-8 is embedded in a poly(ethylene oxide) and Matrimid polymer blend; and that increased hydrothermal stability is realized when the water-sensitive MOF HKUST-1 is embedded in polystyrene fibers relative to pure HKUST-1 powder.
The second technique involves the creation of a pore network throughout the fiber to increase accessibility of embedded sorbent particles. It is demonstrated that the removal of a blended highly soluble polymer additive from the spun particle-containing fibers leaves a pore network behind without removing the embedded sorbent. The increased accessibility of embedded sorbents is validated by embedding a known direct air capture sorbent in porous electrospun fibers, and demonstrating that they have the fastest kinetic uptake of any direct air capture sorbent reported in literature to date, along with over 90% sorbent accessibility.
The first technique involves imbedding sorbent particles inside the fibers: forming particle-embedded fibers. It is demonstrated that particles will spontaneously coat themselves in the fibers at dilute loadings, but at higher loadings some get trapped on the fiber surface. A mathematical model is used to show that when these particles are embedded, the polymeric coating provided by the fibers may be designed to increase the kinetic selectivity and/or stability of the embedded sorbents. Two proof-of-concept studies are performed to validate this model including the increased selectivity of carbon dioxide over nitrogen when the MOF ZIF-8 is embedded in a poly(ethylene oxide) and Matrimid polymer blend; and that increased hydrothermal stability is realized when the water-sensitive MOF HKUST-1 is embedded in polystyrene fibers relative to pure HKUST-1 powder.
The second technique involves the creation of a pore network throughout the fiber to increase accessibility of embedded sorbent particles. It is demonstrated that the removal of a blended highly soluble polymer additive from the spun particle-containing fibers leaves a pore network behind without removing the embedded sorbent. The increased accessibility of embedded sorbents is validated by embedding a known direct air capture sorbent in porous electrospun fibers, and demonstrating that they have the fastest kinetic uptake of any direct air capture sorbent reported in literature to date, along with over 90% sorbent accessibility.
ContributorsArmstrong, Mitchell (Author) / Mu, Bin (Thesis advisor) / Green, Matthew (Committee member) / Seo, Dong (Committee member) / Lackner, Klaus (Committee member) / Holloway, Julianne (Committee member) / Arizona State University (Publisher)
Created2018
Description
The large-scale anthropogenic emission of carbon dioxide into the atmosphere leads to many unintended consequences, from rising sea levels to ocean acidification. While a clean energy infrastructure is growing, mid-term strategies that are compatible with the current infrastructure should be developed. Carbon capture and storage in fossil-fuel power plants is one way to avoid our current gigaton-scale emission of carbon dioxide into the atmosphere. However, for this to be possible, separation techniques are necessary to remove the nitrogen from air before combustion or from the flue gas after combustion. Metal-organic frameworks (MOFs) are a relatively new class of porous material that show great promise for adsorptive separation processes. Here, potential mechanisms of O2/N2 separation and CO2/N2 separation are explored.
First, a logical categorization of potential adsorptive separation mechanisms in MOFs is outlined by comparing existing data with previously studied materials. Size-selective adsorptive separation is investigated for both gas systems using molecular simulations. A correlation between size-selective equilibrium adsorptive separation capabilities and pore diameter is established in materials with complex pore distributions. A method of generating mobile extra-framework cations which drastically increase adsorptive selectivity toward nitrogen over oxygen via electrostatic interactions is explored through experiments and simulations. Finally, deposition of redox-active ferrocene molecules into systematically generated defects is shown to be an effective method of increasing selectivity towards oxygen.
First, a logical categorization of potential adsorptive separation mechanisms in MOFs is outlined by comparing existing data with previously studied materials. Size-selective adsorptive separation is investigated for both gas systems using molecular simulations. A correlation between size-selective equilibrium adsorptive separation capabilities and pore diameter is established in materials with complex pore distributions. A method of generating mobile extra-framework cations which drastically increase adsorptive selectivity toward nitrogen over oxygen via electrostatic interactions is explored through experiments and simulations. Finally, deposition of redox-active ferrocene molecules into systematically generated defects is shown to be an effective method of increasing selectivity towards oxygen.
ContributorsMcIntyre, Sean (Author) / Mu, Bin (Thesis advisor) / Green, Matthew (Committee member) / Lind, Marylaura (Committee member) / Arizona State University (Publisher)
Created2019
Description
A new class of layered materials called the transition metal trichalcogenides (TMTCs) exhibit strong anisotropic properties due to their quasi-1D nature. These 2D materials are composed of chain-like structures which are weakly bound to form planar sheets with highly directional properties. The vibrational properties of three materials from the TMTC family, specifically TiS3, ZrS3, and HfS3, are relatively unknown and studies performed in this work elucidates the origin of their Raman characteristics. The crystals were synthesized through chemical vapor transport prior to mechanical exfoliation onto Si/SiO¬2 substrates. XRD, AFM, and Raman spectroscopy were used to determine the crystallinity, thickness, and chemical signature of the exfoliated crystals. Vibrational modes and anisotropic polarization are investigated through density functional theory calculations and angle-resolved Raman spectroscopy. Particular Raman modes are explored in order to correlate select peaks to the b-axis crystalline direction. Mode III vibrations for TiS3, ZrS3, and HfS3 are shared between each material and serves as a unique identifier of the crystalline orientation in MX3 materials. Similar angle-resolved Raman studies were conducted on the novel Nb0.5Ti0.5S3 alloy material grown through chemical vapor transport. Results show that the anisotropy direction is more difficult to determine due to the randomization of quasi-1D chains caused by defects that are common in 2D alloys. This work provides a fundamental understanding of the vibrational properties of various TMTC materials which is needed to realize applications in direction dependent polarization and linear dichroism.
ContributorsKong, Wilson (Author) / Tongay, Sefaattin (Thesis advisor) / Wang, Liping (Committee member) / Green, Matthew (Committee member) / Arizona State University (Publisher)
Created2017
Description
Two-dimensional quantum materials have garnered increasing interest in a wide
variety of applications due to their promising optical and electronic properties. These
quantum materials are highly anticipated to make transformative quantum sensors and
biosensors. Biosensors are currently considered among one of the most promising
solutions to a wide variety of biomedical and environmental problems including highly
sensitive and selective detection of difficult pathogens, toxins, and biomolecules.
However, scientists face enormous challenges in achieving these goals with current
technologies. Quantum biosensors can have detection with extraordinary sensitivity and
selectivity through manipulation of their quantum states, offering extraordinary properties
that cannot be attained with traditional materials. These quantum materials are anticipated
to make significant impact in the detection, diagnosis, and treatment of many diseases.
Despite the exciting promise of these cutting-edge technologies, it is largely
unknown what the inherent toxicity and biocompatibility of two-dimensional (2D)
materials are. Studies are greatly needed to lay the foundation for understanding the
interactions between quantum materials and biosystems. This work introduces a new
method to continuously monitor the cell proliferation and toxicity behavior of 2D
materials. The cell viability and toxicity measurements coupled with Live/Dead
fluorescence imaging suggest the biocompatibility of crystalline MoS2 and MoSSe
monolayers and the significantly-reduced cellular growth of defected MoTe2 thin films
and exfoliated MoS2 nanosheets. Results show the exciting potential of incorporating
kinetic cell viability data of 2D materials with other assay tools to further fundamental
understanding of 2D material biocompatibility.
variety of applications due to their promising optical and electronic properties. These
quantum materials are highly anticipated to make transformative quantum sensors and
biosensors. Biosensors are currently considered among one of the most promising
solutions to a wide variety of biomedical and environmental problems including highly
sensitive and selective detection of difficult pathogens, toxins, and biomolecules.
However, scientists face enormous challenges in achieving these goals with current
technologies. Quantum biosensors can have detection with extraordinary sensitivity and
selectivity through manipulation of their quantum states, offering extraordinary properties
that cannot be attained with traditional materials. These quantum materials are anticipated
to make significant impact in the detection, diagnosis, and treatment of many diseases.
Despite the exciting promise of these cutting-edge technologies, it is largely
unknown what the inherent toxicity and biocompatibility of two-dimensional (2D)
materials are. Studies are greatly needed to lay the foundation for understanding the
interactions between quantum materials and biosystems. This work introduces a new
method to continuously monitor the cell proliferation and toxicity behavior of 2D
materials. The cell viability and toxicity measurements coupled with Live/Dead
fluorescence imaging suggest the biocompatibility of crystalline MoS2 and MoSSe
monolayers and the significantly-reduced cellular growth of defected MoTe2 thin films
and exfoliated MoS2 nanosheets. Results show the exciting potential of incorporating
kinetic cell viability data of 2D materials with other assay tools to further fundamental
understanding of 2D material biocompatibility.
ContributorsTran, Michael, Ph.D (Author) / Tongay, Sefaattin (Thesis advisor) / Green, Matthew (Thesis advisor) / Muhich, Christopher (Committee member) / Arizona State University (Publisher)
Created2019