Investigating the parameters of metal-organic framework crystal growth control for reverse osmosis membrane nanofillers and direct air capture of CO2

Inorganic nano- and micromaterials (NMMs) exhibit unique properties including high surface areas, tunable optical and electronic properties, low densities, thermal and chemical robustness, and catalytic capabilities, among others. One of the more novel subclasses of NMMs, metal-organic frameworks (MOFs), are crystalline porous coordination polymers consisting of metal nodes connected by organic linkers to form one-, two-, or three-dimensional frameworks. While the mechanism of MOF formation is complex, tuning the metal:ligand ratios, reaction temperature and vessel pressure, ligand concentration, modulator concentration, and H+ activity impacts particle size, morphology, dispersity, and isotropy of these materials. MOFs also exhibit post-synthetic modification capabilities, which, along with their tunable synthetic nature, make them promising candidates for composite materials such as functionalized nanofillers for reverse osmosis (RO) desalination. The work described herein investigates synthetic parameters of a zirconium-based porphyrinic MOF, PCN-222, to selectively control its crystal size, aspect ratio, and dispersity. Size-constrained PCN-222 was post-synthetically modified with fatty acids and zwitterions to be used as RO thin-film composite (TFC) membranes with improved membrane flux, salt rejection, and anti-fouling properties. The synthetic parameters of MOFs were also considered for the commercial scale-up of CO2 direct air capture (DAC) solid sorbents, including UiO-66, MIL-101-Cr, and Mg-MOF-74, to preserve CO2 uptake capacities between lab and industrial scales.

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Chemistry

Department dc:contributor.department

Chemistry

Grantor dc:publisher

Virginia Tech

Year dc:date.issued

2022

Author dc:creator

• Bonnett, Brittany Lauren

Chair dc:contributor.committeechair

• Morris, Amanda

Committee members dc:contributor.committeemember

• Madsen, Louis A.
• Morris, John R.
• Yee, Gordon T.

• metal-organic frameworks
• crystal growth
• nanomaterials
• polymer composites
• reverse osmosis membranes
• CO2 capture

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Language dc:language.iso

en

Dc Identifier Other

vt_gsexam:34482

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/110410