Mixed Matrix Membranes (MMMs) combine a continuous organic polymer phase with a distributed porous additive, i.e. filler, and benefit from the ease processability of polymers as well as the improved gas separation performance of diverse porous filler materials. MMMs may have separation qualities that outperform the selectivity/permeability trade-off reported in pure polymer membranes. All MMMs require a polymer phase and a filler, and in this research a Pebax-1657 is used as a matrix and for filler a Covalent organic framework (COF) as it is less understood. Covalent organic frameworks (COFs) represent a category of porous organic polymers that have garnered significant interest across various fields, including gas adsorption and storage, catalysis, sensing, and photovoltaics. These frameworks offer outstanding characteristics such as permanent porosity, high surface areas, and easily adjustable frameworks [3]. Additionally, their entirely organic composition can lead to enhanced interactions between fillers and polymers, mitigating the formation of nonselective defects during mixed-matrix membrane (MMM) preparation that are often seen with using other sorts of fillers such as silica and metal- organic frameworks (MOFs). Once synthesized the MMMs which are based on COF will be tested in an in house built gas permeance setup to test for single gas permeance, giving us deep insight into the performance of the COF bas MMMs.

My thesis, Design of Hierarchically Porous Materials Containing Covalent Organic Frameworks, focuses on testing the validity of incorporating nanoporous organic materials into macroporous scaffolding to improve the functionality of covalent organic frameworks as materials for filtration applications. The macroporous scaffold was based off of a material recently described in literature and the bulk of the experimentation was focused on the effects of the necessary processing for the creation of the macroporous material on the structure of the covalent organic frameworks. The property primarily investigated was the Brunauer-Emmett-Teller surface area, as the applicability of the frameworks is largely determined by their nanoporous surface area.

Using DFT calculations and GAMESS computational software, porphine and its derivatives were analyzed for unique sites to accept the adsorbates As(III), As(V) and P(V) in order to compare resulting adsorption energies and determine if any of these molecules prefer arsenic oxyanions over phosphate. Pure porphine preferred As(III) over P(V) with a resulting adsorption energy of -0.7974 eV. Of the functionalized porphyrins tested, carboxyl porphyrin preferred As(V) over P(V) with a total adsorption energy of -0.7345 eV. Ethyl, methyl, chlorine and amino porphyrin all preferred As(III), with energies of -0.7934, -0.8239, -0.7602, and -0.8508 eV, respectively. Of the metalated porphyrins tested, copper and vanadium porphyrin preferred As(V) over P(V) with adsorption energies of -0.7645 and -2.0915 eV. Chromium, iron and magnesium porphyrin all preferred As(III) over P(V) with energies of -0.5993, -1.4539, and - 1.0790 eV, respectively.