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
Geology and its tangential studies, collectively known and referred to in this thesis as geosciences, have been paramount to the transformation and advancement of society, fundamentally changing the way we view, interact and live with the surrounding natural and built environment. It is important to recognize the value and importance of this interdisciplinary scientific field while reconciling its ties to imperial and colonizing extractive systems which have led to harmful and invasive endeavors. This intersection among geosciences, (environmental) justice studies, and decolonization is intended to promote inclusive pedagogical models through just and equitable methodologies and frameworks as to prevent further injustices and promote recognition and healing of old wounds. By utilizing decolonial frameworks and highlighting the voices of peoples from colonized and exploited landscapes, this annotated syllabus tackles the issues previously described while proposing solutions involving place-based education and the recentering of land within geoscience pedagogical models. (abstract)
efficient process for selective removal of alcohol from water than distillation. It is
necessary that the membranes have high alcohol permeabilities and selectivities.
Polydimethylsiloxane (PDMS) based mixed matrix membranes (MMMs) have
demonstrated very promising results. Zeolitic imidazolate framework-71 (ZIF-71)
demonstrated promising alcohol separation abilities. In this dissertation, we present
fundamental studies on the synthesis of ZIF-71/PDMS MMMs.
Free-standing ZIF-71/ PDMS membranes with 0, 5, 25 and 40 wt % ZIF-71
loadings were prepared and the pervaporation separation for ethanol and 1-butanol from
water was measured. ZIF-71/PDMS MMMs were formed through addition cure and
condensation cure methods. Addition cure method was not compatible with ZIF-71
resulting in membranes with poor mechanical properties, while the condensation cure
method resulted in membranes with good mechanical properties. The 40 wt % ZIF-71
loading PDMS nanocomposite membranes achieved a maximum ethanol/water selectivity
of 0.81 ± 0.04 selectivity and maximum 1-butnaol/water selectivity of 5.64 ± 0.15.
The effects of synthesis time, temperature, and reactant ratio on ZIF-71 particle
size and the effect of particle size on membrane performance were studied. Temperature
had the greatest effect on ZIF-71 particle size as the synthesis temperature varied from -
20 to 35 ºC. The ZIF-71 synthesized had particle diameters ranging from 150 nm to 1
μm. ZIF-71 particle size is critical in ZIF-71/PDMS composite membrane performance
for alcohol removal from water through pervaporation. The membranes made with
micron sized ZIF-71 particles showed higher alcohol/water selectivity than those with
smaller particles. Both alcohol and water permeability increased when larger sized ZIF-
71 particles were incorporated.
ZIF-71 particles were modified with four ligands through solvent assisted linker
exchange (SALE) method: benzimidazole (BIM), 5-methylbenzimidazole (MBIM), 5,6-
dimethylbenzimidazole (DMBIM) and 4-Phenylimidazole (PI). The morphology of ZIF-
71 were maintained after the modification. ZIF-71/PDMS composite membranes with 25
wt% loading modified ZIF-71 particles were made for alcohol/water separation. Better
particle dispersion in PDMS polymer matrix was observed with the ligand modified ZIFs.
For both ethanol/water and 1-butanol/water separations, the alcohol permeability and
alcohol/water selectivity were lowered after the ZIF-71 ligand exchange reaction.
Static TGA decomposition kinetics studies show that ZIF-8 nanocrystals maintain their crystallinity up to 200○C in inert, oxidizing and reducing atmospheres. At temperatures of 250○C and higher, the findings herein support the postulation that ZIF-8 nanocrystals undergo temperature induced decomposition via thermolytic bond cleaving reactions to form an imidazole-Zn-azirine structure. The crystallinity/bond integrity of ZIF-8 membrane thin films is maintained at temperatures below 150○C.
Ethane and ethylene transport was studied in single and binary gas mixtures. Thermodynamic parameters derived from membrane permeation and crystal adsorption experiments show that the C2 transport mechanism is controlled by adsorption rather than diffusion. Low activation energy of diffusion values for both C2 molecules and limited energetic/entropic diffusive selectivity are observed for C2 molecules despite being larger than the nominal ZIF-8 pore aperture and is due to pore flexibility.
Finally, ZIF-8 membranes were modified with 5,6 dimethylbenzimidazole through solvent assisted membrane surface ligand exchange to narrow the pore aperture for enhanced molecular sieving. Results show that relatively fast exchange kinetics occur at the mainly at the outer ZIF-8 membrane surface between 0-30 minutes of exchange. Short-time exchange enables C3 selectivity increases with minimal olefin permeance losses. As the reaction proceeds, the ligand exchange rate slows as the 5,6 DMBIm linker proceeds into the ZIF-8 inner surface, exchanges with the original linker and first disrupts the original framework’s crystallinity, then increases order as the reaction proceeds. The ligand exchange rate increases with temperature and the H2/C2 separation factor increases with increases in ligand exchange time and temperature.
In this study, high quality graphene oxide membranes are synthesized on polyester track etch substrates by different deposition methods and characterized by XRD, SEM, AFM as well as single gas permeation and binary (H2/CO2) separation experiments. Membranes are made from large graphene oxide sheets of different sizes (33 and 17 micron) using vacuum filtration to shed more light on their transport mechanism. Membranes are made from dilute graphene oxide suspension by easily scalable spray coating technique to minimize extrinsic wrinkle formation. Finally, Brodie’s derived graphene oxide sheets were used to prepare membranes with narrow interlayer spacing to improve their (H2/CO2) separation performance.
An inter-sheet and inner-sheet two-pathway model is proposed to explain the permeation and separation results of graphene oxide membranes obtained in this study. At room temperature, large gas molecules (CH4, N2, and CO2) permeate through inter-sheet pathway of the membranes, exhibiting Knudsen like diffusion characteristics, with the permeance for the small sheet membrane about twice that for the large sheet membrane. The small gases (H2 and He) exhibit much higher permeance, showing significant flow through an inner-sheet pathway, in addition to the flow through the inter-sheet pathway. Membranes prepared by spray coating offer gas characteristics similar to those made by filtration, however using dilute graphene oxide suspension in spray coating will help reduce the formation of extrinsic wrinkles which result in reduction in the porosity of the inter-sheet pathway where the transport of large gas molecules dominates. Brodie’s derived graphene oxide membranes showed overall low permeability and significant improvement in in H2/CO2 selectivity compared to membranes made using Hummers’ derived sheets due to smaller interlayer space height of Brodie’s sheets (~3 Å).
sensors. The unique crystalline structure of MOFs in addition to controllability of
their pore size and their intake selectivity makes them a promising method of detection.
Detection of metal ions in water using a binary mixture of luminescent MOFs
has been reported. 3 MOFs(ZrPDA, UiO-66 and UiO-66-NH2) as detectors and 4
metal ions(Pb2+, Ni2+, Ba2+ and Cu2+) as the target species were chosen based on
cost, water stability, application and end goals.
It is possible to detect metal ions such as Pb2+ at concentrations at low as 0.005
molar using MOFs. Also, based on the luminescence responses, a method of distinguishing
between similar metal ions has been proposed. It is shown that using a
mixture of MOFs with dierent reaction to metal ions can lead to unique and specic
3D luminescence maps, which can be used to identify the present metal ions in water
and their amount.
In addition to the response of a single MOF to addition of a single metal ion,
luminescence response of ZrPDA + UiO-66 mixture to increasing concentration of
each of 4 metal ions was studied, and summarized. A new peak is observed in the
mixture, that did not exist before, and it is proposed that this peak requires metal
ions to activate
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.
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.