Biological systems that perform critical reactions like carbon dioxide reduction, water oxidation, or phosphonate ester hydrolysis consist of many separate components with many different degrees of freedom. While the functionality of pieces of these systems can be replicated synthetically to some degree, the integration of synthetic catalysts into an overall system is a significant challenge that remains in the way of creating artificial enzyme-like systems. Furthermore, being able to tune their environments and their characteristics in-situ is critical to optimizing a potential catalytic system. Metal-Organic Frameworks (MOFs) are porous materials consisting of inorganic linkers and organic nodes that assemble into a crystalline structure. The ability to replace linkers and nodes and thus tune the structure and electronics of these materials makes them ideal for studying how active site properties change with different functionalities or metals. Furthermore, the ability to functionalize this support with additional components gives them great potential for creating complex assemblies that resemble biological systems. There are three basic degrees of freedom present in MOFs: 1) the organic linker and its functionalities, 2) the metal node as support or catalyst, and 3) the porous space itself. The first two have been extensively explored, but the third is the most critical towards building complex assemblies, as it presents an entirely different mode of functionalization to the other two. Overall, this work builds upon previous ideas of using each MOF degree of freedom to make scientifically controlled electronic comparisons for important catalytic reactions like chemical warfare agent hydrolysis (Chapters 3 and 4). However, this work also expands the possibilities for MOF-supported systems by introducing a new functionalization method, namely noncovalent adsorption onto the external or internal surface areas of these frameworks, with the potential for greatly expanding the complexity of components that can be put into a MOF system (Chapter 2). Future development using this method should lead to multi-function, multi-reaction catalytic systems with communicating individual components, effectively leading to the creation of artificial nanoenzymes.

Creator

• Sheridan, Thomas Robert

DOI

• https://doi.org/10.21985/n2-ebxq-9a34

Subject

• Inorganic chemistry

Language

• en

Alternate Identifier

• http://dissertations.umi.com/northwestern:16718
• etdadmin_upload_1012379

Keyword

• Noncovalent functionalization
• Metal-Organic Frameworks
• Energy Transfer
• Hydrolysis
• Chemical Warfare Agents

Date created

• 2023-01-01

Resource type

• Dissertation

Rights statement

• In Copyright