Functionalized Hollow Fibers Spun from Microporous Organic Polymers (MOPs) for Membrane-Based Separations and Carbon Capture
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Jean-Baptiste-pjeanbap-phd-cheme-2026-thesis.pdf
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Author(s)
Jean-Baptiste, Philippe
Advisor(s)
Smith, Zachary P.
Date Issued
May 2026
Publisher
Massachusetts Institute of Technology
Abstract
Separations are an essential part of the chemical industry and are dominated by energy-intensive techniques, which can account for up to 15% of global industrial energy consumption. Membranes have existed as a possible alternative to traditional thermal-based separations. Despite this, polymer membranes see limited use in gas separation applications because of their inherent permeability–selectivity trade-off. To overcome this performance limitation, new polymeric membrane materials known as microporous organic polymers (MOPs) have been developed that incorporate rigid and contorted ladder structures into their backbones, resulting in a high free volume. This includes the archetypical polymer of intrinsic microporosity, PIM-1, as well as more novel spirobifluorene (SBF) based poly(arylene ether) (PAEs). Typically, studies have involved fundamental characterization and performance testing on flat sheet membranes. Unfortunately, a major limitation of this configuration is its lack of scalability, which limits deployment in industrial settings. Along these lines, polymer hollow fibers represent a desirable form factor for industrial gas separation membranes given their substantially higher surface-area-to-volume ratios. This thesis seeks to investigate the post-synthetic modification of PIM-1 hollow fiber membranes via amine functionalization into PIM-NH₂ and track their long term performance. This serves as the first in-depth physical aging study on hollow fibers spun from PIMs by monitoring their gas permeation properties over 2150 hours and comparing their aging behavior to dense films and thin film composites. Furthermore, the spinning of the microporous PAE, SBF-TBTrip-I, into the hollow fiber membrane configuration was investigated, representing the first time this form factor has been reported for this class of SBF-based PAEs and among the first times a microporous polymer has been spun after PIM-1. Lastly, PIM-1 and PIM-NH₂ were further investigated with the addition of zeolites under high temperature activation to manufacture microporous hollow fiber sorbents for the removal of CO₂ from flue gas streams, highlighting the thermal stability of PIMs as well as their versatility in applications outside of membrane-based separations. Collectively, this thesis provides valuable insight into the manufacture of hollow fibers spun from MOPs, their performance over time, and their utility as polymer binders in sorbent composites for CO₂ capture.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
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