Doctoral Dissertations

Date of Award

5-2025

Degree Type

Dissertation

Degree Name

Doctor of Philosophy

Major

Natural Resources

Major Professor

Mi Li

Committee Members

David P. Harper, Micholas D. Smith, Siqun Wang, Mi Li

Abstract

Metal-organic frameworks (MOFs) are a class of crystalline materials that have been of immense interest due to their highly porous nature and multifunctional properties. However, the scalable production and applications of MOFs are hindered by their insolubility in water, tendency to precipitate and aggregate, and lack of processability. The combination of flexible cellulose macromolecules and rigid MOF crystals to form functional composites offers a promising solution to overcome these challenges. While recent studies have witnessed a fast evolution of cellulose/MOF functional material development, interfacial behavior and inherent mechanisms of hybridization between the two phases are relatively less clear. The current dissertation aims to unravel the inherent interaction between the two components and offer guidelines for rational fabrication of functional cellulose/MOF composites. The templating capability of cellulose was first demonstrated by using different modified forms of nanocellulose to hybridize with MOFs. Both sulfonated and carboxylated cellulose successfully directed the in situ formation of MOFs on the fibrils. The sulfonated cellulose/MOF was processed into freestanding aerogels with promising adsorption capacity for methylene blue. In the meantime, carboxylated cellulose templated the growth of fluorescent MOFs, which was subsequently designed into a sensing pad to detect pesticide methyl parathion. To enhance the cellulose/MOF compatibility and processability, the ionic liquid-induced spinning process was used. This enabled MOFs to be evenly incorporated into the regenerated cellulose filament matrix after dissolution and spinning. The interfacial compatibility between cellulose and MOFs was thoroughly investigated from the bulk morphology to the molecular level. Lastly, the mechanism of MOFs assembly on the carboxylated cellulose was investigated using molecular dynamics simulations. It is found that MOF precursors form coordination and hydrogen bonds with cellulose. These interactions provide binding sites for MOFs, guiding the in situ assembly of MOFs on the cellulose matrix.

Download
Files over 3MB may be slow to open. For best results, right-click and select "save as..."

Share

COinS