While highly crystalline porous materials, such as metal-organic frameworks (MOFs), have been heavily studied, their amorphous counterparts have not. This is mainly due to the controllable structures and ease of characterization for crystalline materials, neither of which are typically available for amorphous material. However, despite their difficult characterization, amorphous materials have many potential benefits, particularly related to their combination of high potential stability and tunability. In this work, I focused in on two families of amorphous materials, porous polymer networks (PPNs), and MOF-derived carbons (MOFdCs). I attempted to elucidate ways in which these materials can be analyzed, and how, despite their amorphous nature, they can be tuned for different properties. In the first project, I describe a method of improving the CO2 cycling performance of an amorphous PPN based material through the incorporation of functionalized dopant molecules. In particular, I found that through the incorporation of the hydroxyl-containing cyanuric acid, which can engage in hydrogen bonding interactions with the loaded active amine species, I could achieve improved CO2 cycling capacity (<4% loss in uptake performance) over 30 cycles. In addition, through in situ IR spectroscopy, it was shown that this PPN, PPN-151-DETA, engages in a stronger chemisorptive mechanism relative to the non-cyanuric acid doped material. In the second project, I investigated the effect of the gas environment on the calcination of an iron-based MOF, PCN-250, to produce a MOFdC. I showed that the resulting iron oxide phase and level of porosity are both dependent on the particular gas environment during calcination. In addition, I showed it was possible to investigate the structure of the porous carbon through neutron total scattering and pair distribution (PDF) methodologies, indicating that the residual carbon exists in the graphitic phase. This work was continued in the final project, wherein I investigated both a Zn (Zn-MOF-74) and Zr (UiO 66) based MOF under variable temperature calcination. Neutron total scattering again showed the presence of graphitic carbon, with the degree of structural order in the graphitic phase being dependent on the temperature of calcination. Finally, I showed that the cubic zirconium cluster in UiO-66 was able to act as a template for the formation of higher-order zirconia phases in the resulting carbon. These projects all show the potential that amorphous materials have for unique properties and gives insight into some of the structural features of this often-neglected class of materials.
