Doctoral Dissertations

Date of Award

12-2019

Degree Type

Dissertation

Degree Name

Doctor of Philosophy

Major

Chemical Engineering

Major Professor

Bamin Khomami

Committee Members

Dibyendu Mukherjee, Paul Frymier, Craig Barnes

Abstract

Metal-organic frameworks (MOFs) are a new type of hybrid material with unique properties that allow for diverse functionality and have shown promise for use in gas storage and separation, catalysis, chemical sensors, supercapacitors, drug delivery, and proton conduction in membranes for fuel cells. Metal ion nodes are connected by organic struts to create infinite crystalline porous networks with tunable geometries and chemical functionalities that have led to more than 20,000 different MOF structures reported in the past decade. These lattices have uniform pore sizes that can range from 0.4 to 10 nm and have set new records for free volume and internal surface area. MOFs offer unique advantages as a porous material over purely inorganic crystallines, such as zeolites, and purely organic aerogels or polymers. The atomic positions of the lattice can be known at the sub-angstrom level, determined almost exclusively by the coordination geometry of the metal node and the topology of the organic linker. Additionally, the chemical composition of the structure can be altered one functional group at a time via pre- or post-synthetic modification of the linkers. This leads to the ability to finely control both the geometry and chemistry of the MOFs; as form begets function, all mechanical, chemical, optical, and electrical properties can be rationally tuned. The vast majority of research on MOFs has centered around their microporosity. The ability to create very small, uniform pores potentially allows for more efficient means of gas and liquid separation. Because this is a new material, the idea of optimizing the already exceptional properties of MOFs is appealing. Due the immense number of possible combinations of metal nodes and organic linkers, there is indication that they hold true promise for utilization in electronic and optoelectronic devices. We have proposed and executed a new method for embedding, protecting, and activating the Photosystem I protein complex inside the ZIF-8 framework.

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