Matching Items (3)
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- All Subjects: Materials
- Creators: Adams, James
Description
Within recent years, metal-organic frameworks, or MOF’s, have gained a lot of attention in the materials research community. These micro-porous materials are constructed of a metal oxide core and organic linkers, and have a wide-variety of applications due to their extensive material characteristic possibilities. The focus of this study is the MOF-5 material, specifically its chemical stability in air. The MOF-5 material has a large pore size of 8 Å, and aperture sizes of 15 and 12 Å. The pore size, pore functionality, and physically stable structure makes MOF-5 a desirable material. MOF-5 holds applications in gas/liquid separation, catalysis, and gas storage. The main problem with the MOF-5 material, however, is its instability in atmospheric air. This inherent instability is due to the water in air binding to the zinc-oxide core, effectively changing the material and its structure. Because of this material weakness, the MOF-5 material is difficult to be utilized in industrial applications. Through the research efforts proposed by this study, the stability of the MOF-5 powder and membrane were studied. MOF-5 powder and a MOF-5 membrane were synthesized and characterized using XRD analysis. In an attempt to improve the stability of MOF-5 in air, methyl groups were added to the organic linker in order to hinder the interaction of water with the Zn4O core. This was done by replacing the terepthalic acid organic linker with 2,5-dimethyl terephthalic acid in the powder and membrane synthesis steps. The methyl-modified MOF-5 powder was found to be stable after several days of exposure to air while the MOF-5 powder exhibited significant crystalline change. The methyl-modified membrane was found to be unstable when synthesized using the same procedure as the MOF-5 membrane.
ContributorsAnderson, Anthony David (Author) / Lin, Jerry Y.S. (Thesis director) / Ibrahim, Amr (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
The story of graphene truly began in what was simply a stub in the journal Physical Review not two years after the end of World War II. In 1947, McGill University physicist P.R. Wallace authored “The Band Theory of Graphite” and attempted to develop a foundation on which the structure-property relationship of graphite could be explored; he calculates the number of free electrons and conductivity of what he describes as “a single hexagonal layer” and “suppos[es] that conduction takes place only in layers” in bulk graphite to predict wave functions, energies at specific atomic sites in the hexagonal lattice, and energy contours using a tight binding approximation for a hypothesized version of what we now call ‘armchair-style’ graphene. While Wallace was the first to explore the band structure and Brillouin Zones of single-layer graphite, the concept of two-dimensional materials was not new. In fact, for years, it was dismissed as a thermodynamic impossibility.
Everything seemed poised against any proposed physical and experimental stability of a structure like graphene. “Thermodynamically impossible”– a not uncommon shutdown to proposed novel physical or chemical concepts– was once used to describe the entire field of proposed two-dimensional crystals functioning separately from a three-dimensional base or crystalline structure. Rudolf Peierls and Lev Davoidovich Landau, both very accomplished physicists respectively known for the Manhattan Project and for developing a mathematical theory of helium superfluidity, rejected the possibility of isolated monolayer to few-layered crystal lattices. Their reasoning was that diverging thermodynamic-based crystal lattice fluctuations would render the material unstable regardless of controlled temperature. This logic is flawed, but not necessarily inaccurate– diamond, for instance, is thermodynamically metastable at room temperature and pressure in that there exists a slow (i.e. slow on the scale of millions of years) but continuous transformation to graphite. However, this logic was used to support an explanation of thermodynamic impossibility that was provided for graphene’s lack of isolation as late as 1979 by Cornell solid-state physicist Nathaniel David Mermin. These physicists’ claims had clear and consistent grounding in experimental data: as thin films become thinner, there exists a trend of a decreasing melting temperature and increasing instability that renders the films into islands at somewhere around ten to twenty atomic layers. This is driven by the thermodynamically-favorable minimization of surface energy.
Everything seemed poised against any proposed physical and experimental stability of a structure like graphene. “Thermodynamically impossible”– a not uncommon shutdown to proposed novel physical or chemical concepts– was once used to describe the entire field of proposed two-dimensional crystals functioning separately from a three-dimensional base or crystalline structure. Rudolf Peierls and Lev Davoidovich Landau, both very accomplished physicists respectively known for the Manhattan Project and for developing a mathematical theory of helium superfluidity, rejected the possibility of isolated monolayer to few-layered crystal lattices. Their reasoning was that diverging thermodynamic-based crystal lattice fluctuations would render the material unstable regardless of controlled temperature. This logic is flawed, but not necessarily inaccurate– diamond, for instance, is thermodynamically metastable at room temperature and pressure in that there exists a slow (i.e. slow on the scale of millions of years) but continuous transformation to graphite. However, this logic was used to support an explanation of thermodynamic impossibility that was provided for graphene’s lack of isolation as late as 1979 by Cornell solid-state physicist Nathaniel David Mermin. These physicists’ claims had clear and consistent grounding in experimental data: as thin films become thinner, there exists a trend of a decreasing melting temperature and increasing instability that renders the films into islands at somewhere around ten to twenty atomic layers. This is driven by the thermodynamically-favorable minimization of surface energy.
ContributorsShulman, Neal Arthur (Author) / Adams, James (Thesis director) / Islam, Rafiqul (Committee member) / Materials Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
Description
Metal-organic frameworks (MOFs) are a new set of porous materials comprised of metals or metal clusters bonded together in a coordination system by organic linkers. They are becoming popular for gas separations due to their abilities to be tailored toward specific applications. Zirconium MOFs in particular are known for their high stability under standard temperature and pressure due to the strength of the Zirconium-Oxygen coordination bond. However, the acid modulator needed to ensure long range order of the product also prevents complete linker deprotonation. This leads to a powder product that cannot easily be incorporated into continuous MOF membranes. This study therefore implemented a new bi-phase synthesis technique with a deprotonating agent to achieve intergrowth in UiO-66 membranes. Crystal intergrowth will allow for effective gas separations and future permeation testing. During experimentation, successful intergrown UiO-66 membranes were synthesized and characterized. The degree of intergrowth and crystal orientations varied with changing deprotonating agent concentration, modulator concentration, and ligand:modulator ratios. Further studies will focus on achieving the same results on porous substrates.
ContributorsClose, Emily Charlotte (Author) / Mu, Bin (Thesis director) / Shan, Bohan (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-12