Premium
Leveraging Free Volume Manipulation to Improve the Membrane Separation Performance of Amine‐Functionalized PIM‐1
Author(s) -
Mizrahi Rodriguez Katherine,
Lin Sharon,
Wu Albert X.,
Han Gang,
Teesdale Justin J.,
Doherty Cara M.,
Smith Zachary P.
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202012441
Subject(s) - selectivity , polymer , sorption , amine gas treating , membrane , chemistry , volume (thermodynamics) , permeability (electromagnetism) , chemical engineering , polymer chemistry , combinatorial chemistry , materials science , organic chemistry , catalysis , thermodynamics , adsorption , biochemistry , physics , engineering
Gas‐separation polymer membranes display a characteristic permeability–selectivity trade‐off that has limited their industrial use. The most comprehensive approach to improving performance is to devise strategies that simultaneously increase fractional free volume, narrow free volume distribution, and enhance sorption selectivity, but generalizable methods for such approaches are exceedingly rare. Here, we present an in situ crosslinking and solid‐state deprotection method to access previously inaccessible sorption and diffusion characteristics in amine‐functionalized polymers of intrinsic microporosity. Free volume element (FVE) size can be increased while preserving a narrow FVE distribution, enabling below‐upper bound polymers to surpass the H 2 /N 2 , H 2 /CH 4 , and O 2 /N 2 upper bounds and improving CO 2 ‐based selectivities by 200 %. This approach can transform polymers into chemical analogues with improved performance, thereby overcoming traditional permeability–selectivity trade‐offs.