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New insights into the pore development mechanism of layered hydroxides upon thermal activation

Description

Layered double hydroxides (LDHs), also known as hydrotalcite-like materials, are extensively used as precursors for the preparation of (photo-)catalysts, electrodes, magnetic materials, sorbents, etc. The synthesis typically involves the transformation to the corresponding mixed metal oxide via calcination, resulting in

Layered double hydroxides (LDHs), also known as hydrotalcite-like materials, are extensively used as precursors for the preparation of (photo-)catalysts, electrodes, magnetic materials, sorbents, etc. The synthesis typically involves the transformation to the corresponding mixed metal oxide via calcination, resulting in atomically dispersed mixed metal oxides (MMOs). This process alters the porosity of the materials, with crucial implications for the performance in many applications. Yet, the mechanisms of pore formation and collapse are poorly understood. Combining an integrated in situ and ex situ characterization approach, here we follow the evolution of porosity changes during the thermal decomposition of LDHs integrating different divalent (Mg, Ni) and trivalent (Al, Ga) metals. Variations in porous properties determined by high-resolution argon sorption are linked to the morphological and compositional changes in the samples by in situ transmission electron microscopy coupled with energy dispersive X-ray spectroscopy, which is facilitated by the synthesis of well crystallized LDHs of large crystal size. The observations are correlated with the phase changes identified by X-ray diffraction, the mass losses evidenced by thermogravimetric analysis, the structural changes determined by infrared and nuclear magnetic resonance spectroscopy, and the pore connectivity analyzed by positron annihilation spectroscopy. The findings show that the multimetallic nature of the LDH governs the size and distribution (geometry, location, and connectivity) of the mesopores developed, which is controlled by the crystallization of the MMO phase, providing key insights for the improved design of porous mixed metal oxides.

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2017-05

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Carbonate-ceramic dual-phase membranes for high temperature carbon dioxide separation

Description

Emission of CO2 into the atmosphere has become an increasingly concerning issue as we progress into the 21st century Flue gas from coal-burning power plants accounts for 40% of all carbon dioxide emissions. The key to successful separation

Emission of CO2 into the atmosphere has become an increasingly concerning issue as we progress into the 21st century Flue gas from coal-burning power plants accounts for 40% of all carbon dioxide emissions. The key to successful separation and sequestration is to separate CO2 directly from flue gas (10-15% CO2, 70% N2), which can range from a few hundred to as high as 1000°C. Conventional microporous membranes (carbons/silicas/zeolites) are capable of separating CO2 from N2 at low temperatures, but cannot achieve separation above 200°C. To overcome the limitations of microporous membranes, a novel ceramic-carbonate dual-phase membrane for high temperature CO2 separation was proposed. The membrane was synthesized from porous La0.6Sr0.4Co0.8Fe0.2O3-d (LSCF) supports and infiltrated with molten carbonate (Li2CO3/Na2CO3/K2CO3). The CO2 permeation mechanism involves a reaction between CO2 (gas phase) and O= (solid phase) to form CO3=, which is then transported through the molten carbonate (liquid phase) to achieve separation. The effects of membrane thickness, temperature and CO2 partial pressure were studied. Decreasing thickness from 3.0 to 0.375 mm led to higher fluxes at 900°C, ranging from 0.186 to 0.322 mL.min-1.cm-2 respectively. CO2 flux increased with temperature from 700 to 900°C. Activation energy for permeation was similar to that for oxygen ion conduction in LSCF. For partial pressures above 0.05 atm, the membrane exhibited a nearly constant flux. From these observations, it was determined that oxygen ion conductivity limits CO2 permeation and that the equilibrium oxygen vacancy concentration in LSCF is dependent on the partial pressure of CO2 in the gas phase. Finally, the dual-phase membrane was used as a membrane reactor. Separation at high temperatures can produce warm, highly concentrated streams of CO2 that could be used as a chemical feedstock for the synthesis of syngas (H2 + CO). Towards this, three different membrane reactor configurations were examined: 1) blank system, 2) LSCF catalyst and 3) 10% Ni/y-alumina catalyst. Performance increased in the order of blank system < LSCF catalyst < Ni/y-alumina catalyst. Favorable conditions for syngas production were high temperature (850°C), low sweep gas flow rate (10 mL.min-1) and high methane concentration (50%) using the Ni/y-alumina catalyst.

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2011

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Synthesis and stability of ceramic-carbonate dual-phase membrane for carbon dioxide separation

Description

Of the potential technologies for pre-combustion capture, membranes offer the advantages of being temperature resistant, able to handle large flow rates, and having a relatively small footprint. A significant amount of research has centered on the use of polymeric and

Of the potential technologies for pre-combustion capture, membranes offer the advantages of being temperature resistant, able to handle large flow rates, and having a relatively small footprint. A significant amount of research has centered on the use of polymeric and microporous inorganic membranes to separate CO2. These membranes, however, have limitations at high temperature resulting in poor permeation performance. To address these limitations, the use of a dense dual-phase membrane has been studied. These membranes are composed of conductive solid and conductive liquid phases that have the ability to selectively permeate CO2 by forming carbonate ions that diffuse through the membrane at high temperature. The driving force for transport through the membrane is a CO2 partial pressure gradient. The membrane provides a theoretically infinite selectivity. To address stability of the ceramic-carbonate dual-phase membrane for CO2 capture at high temperature, the ceramic phase of the membrane was studied and replaced with materials previously shown to be stable in harsh conditions. The permeation properties and stability of La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF)-carbonate, La0.85Ce0.1Ga0.3Fe0.65Al0.05O3-δ (LCGFA)-carbonate, and Ce0.8Sm0.2O1.9 (SDC)-carbonate membranes were examined under a wide range of experimental conditions at high temperature. LSCF-carbonate membranes were shown to be unstable without the presence of O2 due to reaction of CO2 with the ceramic phase. In the presence of O2, however, the membranes showed stable permeation behavior for more than one month at 900oC. LCGFA-carbonate membranes showed great chemical and permeation stability in the presence of various conditions including exposure to CH4 and H2, however, the permeation performance was quite low when compared to membranes in the literature. Finally, SDC-carbonate membranes showed great chemical and permeation stability both in a CO2:N2 environment for more than two weeks at 900oC as well as more than one month of exposure to simulated syngas conditions at 700oC. Ceramic phase chemical stability increased in the order of LSCF < LCGFA < SDC while permeation performance increased in the order of LCGFA < LSCF < SDC.

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2013

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Synthesis and Characterization of 2D Metal-organic Frameworks for Mixed-matrix Membrane Gas Separations

Description

Membrane-based technology for gas separations is currently at an emerging stage of advancement and adoption for environmental and industrial applications due to its substantial advantages like lower energy and operating costs over the conventional gas separation technologies. Unfortunately, the available

Membrane-based technology for gas separations is currently at an emerging stage of advancement and adoption for environmental and industrial applications due to its substantial advantages like lower energy and operating costs over the conventional gas separation technologies. Unfortunately, the available polymeric (or organic) membranes suffer a trade-off between permeance and selectivity. Mixed matrix membranes (MMMs) containing two-dimensional (2D) metal-organic frameworks (MOFs) as fillers are a highly sought approach to redress this trade-off given their enhanced gas permeabilities and selectivities compared to the pure polymeric membrane. These MMMs are increasingly gaining attention by researchers due to their unique properties and wide small- and large-scale gas separation applications. However, straightforward and scalable methods for the synthesis of MOFs nanosheets have thus far been persistently elusive. This study reports the single-phase preparation, and characterization of MMMs with 2D MOFs nanosheets as fillers. The prepared MOF and the polymer matrix form the ‘dense’ MMMs which exhibit increased gas diffusion resistance, and thus improved separation abilities. The single-phase approach was more successful than the bi-phase at synthesizing the MOFs. The influence of sonication power and time on the characteristics and performance of the membranes are examined and discussed. Increasing the sonication power from 50% to 100% reduces the pore size. Additionally, the ultimate effect on the selectivity and permeance of the MMMs with different single gases is reported. Analysis of results with various gas mixers indicates further performance improvements in these MMMs could be achieved by increasing sonication time and tuning suitable membrane thicknesses. Reported results reveal that MMMs are excellent candidates for next-generation gas mixture separations, with potential applications in CO2 capture and storage, hydrogen recovery, alkene recovery from alkanes, and natural gas purification.

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2019-05

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Synthesis and characterization of boronic-acid-containing metal organic frameworks

Description

We report the synthesis of novel boronic acid-containing metal-organic frameworks (MOFs), which was synthesized via solvothermal synthesis of cobalt nitride with 3,5-Dicarboxyphenylboronic acid (3,5-DCPBC). Powder X-ray diffraction and BET surface area analysis have been used to verify the successful synthesis

We report the synthesis of novel boronic acid-containing metal-organic frameworks (MOFs), which was synthesized via solvothermal synthesis of cobalt nitride with 3,5-Dicarboxyphenylboronic acid (3,5-DCPBC). Powder X-ray diffraction and BET surface area analysis have been used to verify the successful synthesis of this microporous material.

We have also made the attempts of using zinc nitride and copper nitride as metal sources to synthesize the boronic acid-containing MOFs. However, the attempts were not successful. The possible reason is the existence of copper and zinc ions catalyzed the decomposition of 3,5-Dicarboxyphenylboronic acid, forming isophthalic acid. The ended product has been proved to be isophthalic acid crystals by the single crystal X-ray diffraction. The effects of solvents, reaction temperature, and added bases were investigated. The addition of triethylamine has been shown to tremendously improve the sample crystallinity by facilitating ligand deprotonation

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Date Created
2014

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Development of mehanochemically active polymers for early damage detection

Description

Identification of early damage in polymer composite materials is of significant importance so that preventative measures can be taken before the materials reach catastrophic failure. Scientists have been developing damage detection technologies over many years and recently, mechanophore-based polymers, in

Identification of early damage in polymer composite materials is of significant importance so that preventative measures can be taken before the materials reach catastrophic failure. Scientists have been developing damage detection technologies over many years and recently, mechanophore-based polymers, in which mechanical energy is translated to activate a chemical transformation, have received increasing attention. More specifically, the damage can be made detectable by mechanochromic polymers, which provide a visible color change upon the scission of covalent bonds under stress. This dissertation focuses on the study of a novel self-sensing framework for identifying early and in-situ damage by employing unique stress-sensing mechanophores. Two types of mechanophores, cyclobutane and cyclooctane, were utilized, and the former formed from cinnamoyl moeities and the latter formed from anthracene upon photodimerization. The effects on the thermal and mechanical properties with the addition of the cyclobutane-based polymers into epoxy matrices were investigated. The emergence of cracks was detected by fluorescent signals at a strain level right after the yield point of the polymer blends, and the fluorescence intensified with the accumulation of strain. Similar to the mechanism of fluorescence emission from the cleavage of cyclobutane, the cyclooctane moiety generated fluorescent emission with a higher quantum yield upon cleavage. The experimental results also demonstrated the success of employing the cyclooctane type mechanophore as a potential force sensor, as the fluorescence intensification was correlated with the strain increase.

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2014

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Synthesis and characterization of microporous inorganic membranes for propylene/propane separation

Description

Membrane-based gas separation is promising for efficient propylene/propane (C3H6/C3H8) separation with low energy consumption and minimum environment impact. Two microporous inorganic membrane candidates, MFI-type zeolite membrane and carbon molecular sieve membrane (CMS) have demonstrated excellent thermal and chemical stability. Application

Membrane-based gas separation is promising for efficient propylene/propane (C3H6/C3H8) separation with low energy consumption and minimum environment impact. Two microporous inorganic membrane candidates, MFI-type zeolite membrane and carbon molecular sieve membrane (CMS) have demonstrated excellent thermal and chemical stability. Application of these membranes into C3H6/C3H8 separation has not been well investigated. This dissertation presents fundamental studies on membrane synthesis, characterization and C3H6/C3H8 separation properties of MFI zeolite membrane and CMS membrane.

MFI zeolite membranes were synthesized on α-alumina supports by secondary growth method. Novel positron annihilation spectroscopy (PAS) techniques were used to non-destructively characterize the pore structure of these membranes. PAS reveals a bimodal pore structure consisting of intracrystalline zeolitic micropores of ~0.6 nm in diameter and irregular intercrystalline micropores of 1.4 to 1.8 nm in size for the membranes. The template-free synthesized membrane exhibited a high permeance but a low selectivity in C3H6/C3H8 mixture separation.

CMS membranes were synthesized by coating/pyrolysis method on mesoporous γ-alumina support. Such supports allow coating of thin, high-quality polymer films and subsequent CMS membranes with no infiltration into support pores. The CMS membranes show strong molecular sieving effect, offering a high C3H6/C3H8 mixture selectivity of ~30. Reduction in membrane thickness from 500 nm to 300 nm causes an increase in C3H8 permeance and He/N2 selectivity, but a decrease in the permeance of He, N2 and C3H6 and C3H6/C3H8 selectivity. This can be explained by the thickness dependent chain mobility of the polymer film resulting in final carbon membrane of reduced pore size with different effects on transport of gas of different sizes, including possible closure of C3H6-accessible micropores.

CMS membranes demonstrate excellent C3H6/C3H8 separation performance over a wide range of feed pressure, composition and operation temperature. No plasticization was observed at a feed pressure up to 100 psi. The permeation and separation is mainly controlled by diffusion instead of adsorption. CMS membrane experienced a decline in permeance, and an increase in selectivity over time under on-stream C3H6/C3H8 separation. This aging behavior is due to the reduction in effective pore size and porosity caused by oxygen chemisorption and physical aging of the membrane structure.

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Date Created
2015

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Stress-responsive nano- and microcomposites featuring mechanophore units

Description

The problem of catastrophic damage purveys in any material application, and minimizing its occurrence is paramount for general health and safety. Thus, novel damage detection schemes are required that can sense the precursors to damage. Mechanochemistry is the area of

The problem of catastrophic damage purveys in any material application, and minimizing its occurrence is paramount for general health and safety. Thus, novel damage detection schemes are required that can sense the precursors to damage. Mechanochemistry is the area of research that involves the use of mechanical force to induce a chemical change, with recent study focusing on directing the mechanical force to embedded mechanophore units for a targeted chemical response. Mechanophores are molecular units that provide a measureable signal in response to an applied force, often in the form of a visible color change or fluorescent emission, and their application to thermoset network polymers has been limited. Following preliminary work on polymer blends of cyclobutane-based mechanophores and epoxy, dimeric 9-anthracene carboxylic acid (Di-AC)-based mechanophore particles were synthesized and employed to form stress sensitive particle reinforced epoxy matrix composites.

Under an applied stress, the cyclooctane-rings in the Di-AC particles revert back to their fluorescent anthracene form, which linearly enhances the overall fluorescence of the composite in response to the applied strain. The fluorescent signal further allows for stress sensing in the elastic region of the stress-strain curve, which is considered to be a form of damage precursor detection. This behavior was further analyzed at the molecular scale with corresponding molecular dynamics simulations. Following the successful application of Di-AC to an epoxy matrix, the mechanophore particles were incorporated into a polyurethane matrix to show the universal nature of Di-AC as a stress-sensitive particle filler. Interestingly, in polyurethane Di-AC could successfully detect damage with less applied strain compared to the epoxy system.

While mechanophores of varying chemistries have been covalently incorporated into elastomeric and thermoplastic polymer systems, they have not yet been covalently incorporated a thermoset network polymer. Thus, following the study of mechanophore particles as stress-sensitive fillers, two routes of grafting mechanophore units into an epoxy system to form a self-sensing nanocomposite were explored. These involved the mechanophore precursor and mechanophore, cinnamamide and di-cinnamamide, respectively. With both molecules, the free amine groups can directly bond to epoxy resin to covalently incorporate themselves within the thermoset network to form a self-sensing nanocomposite.

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Date Created
2016

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A novel mobile device for environmental hydrocarbon sensing and its applications

Description

The accurate and fast determination of organic air pollutants for many applications and studies is critical. Exposure to volatile organic compounds (VOCs) has become an important public health concern, which may induce a lot of health effects such as respiratory

The accurate and fast determination of organic air pollutants for many applications and studies is critical. Exposure to volatile organic compounds (VOCs) has become an important public health concern, which may induce a lot of health effects such as respiratory irritation, headaches and dizziness. In order to monitor the personal VOCs exposure level at point-of-care, a wearable real time monitor for VOCs detection is necessary. For it to be useful in real world application, it requires low cost, small size and weight, low power consumption, high sensitivity and selectivity.

To meet these requirements, a novel mobile device for personal VOCs exposure monitor has been developed. The key sensing element is a disposable molecularly imprinted polymer based quartz tuning fork resonator. The sensor and fabrication protocol are low cost, reproducible and stable. Characterization on the sensing material and device has been done. Comparisons with gold standards in the field such as GC-MS have been conducted. And the device’s functionality and capability have been validated in field tests, proving that it’s a great tool for VOCs monitoring under different scenarios.

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Date Created
2017

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Development of environmentally responsive multifunctional microgel particles: synthesis, characterization and applications

Description

Environmentally responsive microgels have drawn significant attention due to their intrinsic ability to change volume in response to various external stimuli such as pH, temperature, osmotic pressure, or electric and magnetic fields. The extent of particle swelling is controlled by

Environmentally responsive microgels have drawn significant attention due to their intrinsic ability to change volume in response to various external stimuli such as pH, temperature, osmotic pressure, or electric and magnetic fields. The extent of particle swelling is controlled by the nature of the polymer-solvent interaction. This thesis focuses on design and synthesis of environmentally responsive microgels and their composites, and encompasses methods of utilizing microgel systems in applications as vehicles for the adsorption, retention, and targeted delivery of chemical species. Furthermore, self-assembled microgel particles at ionic liquid (IL)-water interfaces demonstrate responsive colloidal lattice morphology. The thesis first reports on the fundamental aspects of synthesis, functionalization, and characteristic properties of multifunctional environmentally responsive microgels derived from poly(N-isopropylacrylamide) (PNIPAm) and other functional co-monomers. In particular, the uptake and release of active chemical species such as rheology modifiers into and from these ionic microgels is demonstrated. Moreover, a facile tunable method for the formation of organic-inorganic composites with Fe3O4 nanoparticles adsorbed and embedded within ionic microgel particles is explored. Additionally, the development of zwitterionic microgels (ZI-MG) is presented. These aqueous ZI-MG dispersions exhibit reversible parabolic swelling as a function of pH and display a minimum hydrodynamic diameter at a tunable isoelectric point (IEP). This study also elucidates the controlled uptake and release of surfactants from these particle systems. The extent of surfactant loading and the ensuing relative swelling/deswelling behaviors within the polymer networks are explained in terms of their binding interactions. The latter part of this thesis highlights the versatility of fluorescently labeled microgel particles as stabilizers for IL-water droplets. When the prepared particles form monolayers and equilibrate at the liquid-liquid interface, the colloidal lattice organization may re-order itself depending on the surface charge of these particles. Finally, it is shown that the spontaneously formed and densely packed layers of microgel particles can be employed for extraction applications, as the interface remains permeable to small active species.

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Date Created
2015