Nanostructured Hypercrosslinked Porous Organic Polymers: Morphological Evolution and Rapid Separation of Polar Organic Micropollutants.

Nanostructured hypercrosslinked porous organic polymers have triggered immense research interest for a broad spectrum of applications ranging from catalysis to molecular separation. However, it still remains a challenge to tune their nanoscale morphology. Herein, we demonstrated a remarkable variation of morphologies of triptycene-based hypercrosslinked microporous polymers starting from irregular aggregates (FCTP) to rigid spheres (SCTP) to two-dimensional nanosheets (SKTP) from three distinct polymerization methodologies, Friedel-Crafts knitting using an external crosslinker, Scholl reaction, and solvent knitting, respectively. Further, the dramatic role of reaction temperatures, catalysts, and solvents resulting in well-defined morphologies was elucidated. Mechanistic investigations coupled with microscopic and computational studies revealed the evolution of 2D nanosheets of a highly porous solvent-knitted polymer (SKTP, 2385 m g), resulting from the sequential hierarchical self-assembly of nanospheres and nanoribbons. A structure-activity correlation of hypercrosslinked polymers and their sulfonated counterparts for the removal of toxic polar organic micropollutants from water was delineated based on the chemical functionalities, specific surface area, pore size distribution, dispersity, and nanoscale morphology. Furthermore, a sulfonated 2D sheet-like solvent-knitted polymer (SKTPS) exhibited rapid adsorption kinetics (within 30 s) for a large array of polar organic micropollutants, including plastic components, steroids, antibiotic drugs, herbicides, and pesticides with remarkable uptake capacity and excellent recyclability. The current study provides the impetus for designing morphology-controlled functionalized porous polymers for task-specific applications.