Efficient and Accurate Incorporation of Flexibility and Defects Into the Modeling of Adsorption in Metal-Organic Frameworks

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YU-DISSERTATION-2023.pdf (7.07 MB)
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Yu, Zhenzi
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School of Chemical and Biomolecular Engineering
School established in 1901 as the School of Chemical Engineering; in 2003, renamed School of Chemical and Biomolecular Engineering
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https://hdl.handle.net/1853/72695
Abstract
Metal-organic frameworks (MOFs) are crystalline nanoporous materials characterized by the presence of organic linkers connected to metal clusters. Although MOFs inherently exhibit flexibility and contain defects, conventional approaches in high throughput computational screening of MOFs generally assume their structures to be rigid and defect-free. The present thesis addresses this limitation by first conducting a comprehensive assessment of flexibility modeling for MOFs and exploring tools that facilitate the incorporation of flexibility into simulations. We investigated the influence of flexibility on adsorption properties using a set of 15 MOFs, thereby acquiring quantitative insights. Additionally, we established a database of defective MOFs and devised accompanying tools for generating the requisite structures. We introduce the concept of a MOF’s maximum possible defect concentration and obtain quantitative insights into the influence of defects on adsorption. With the successful development of the models, we employed DMOF-1 as a case study to demonstrate how our models assist in bridging the gap between experimental observations and simulation results for a specific MOF. Through the combination of a flexible defective model with experimental data, we propose that the degradation of DMOF-1 by water arises from water adsorption at defective sites within the MOF. Lastly, given the computationally intensive nature of these investigations, we present preliminary outcomes utilizing machine learning to predict the influence of MOF flexibility and defects. This approach leverages information from adsorption properties predicted using rigid and defect-free structures, as well as other pertinent characteristics of the adsorbates and MOFs.
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2023-07-24
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