Boosted Intracavity Aperture in Macrocyclic Amines Enabling Finely Regulated Microporous Membranes

Finely tuning the pore structure of traditional nanofiltration (NF) membranes is challenging but highly effective for achieving efficient separations. Herein, we propose a concept of using macrocyclic amines (1,4,7-triazacyclononane, 3A; 1,4,7,10-tetraazacyclododecane, 4A1; and 1,4,8,11-tetraazacyclotetradecane, 4A2) with different intra-annular apertures to finely modulate the pore structure of microporous membranes via interfacial polymerization (IP). The boost in the intracavity size of the building blocks results in heightened steric hindrance of these amine monomers, leading to a controlled increase in membrane pore size, as demonstrated by both film characterizations and multiscale simulations. In conjunction with the increased intracavity size, the water permeability follows an augmented trend of 3A-TMC, 4A1-TMC, and 4A2-TMC (TMC: trimesoyl chloride) while exhibiting increased molecular weight cut-offs due to larger free-volume elements and stronger pore interconnectivity. Our proposed macrocyclic amine design strategy provides a guideline for finely regulated microporous membranes with high potential in NF-related applications.