Efficient construction of high-quality sulfonated porous aromatic frameworks by optimizing the swelling state of porous structures

Abstract

Conventional post-modification methods usually face the fundamental challenge of balancing the high content of functional groups and large surface area for porous organic polymers (POPs). The reason, presumably, stems from ineffective and insufficient swelling of the porous structure of POP materials, which is detrimental to mass transfer and modification of functional groups, especially with large-sized ones. It is important to note that significant differences exist in the porous structures of POP materials in a solvent-free state after thermal activation and solvent swelling state. Herein, we propose that the improvement of the swelling state of the porous structure of POP materials is more conducive to obtaining high-quality sulfonated POP materials, and employ a one-pot modification strategy for preparing sulfonated porous aromatic frameworks (PAFs) to prove the proposal. These results show that the specific surface area of the resulting polymer is 580 m² g⁻¹ with a sulfur content of up to 13.2 wt%, which is superior to most sulfonated porous materials and the control sample. More importantly, we have also shown that the same conclusion is reached by performing similar treatments on hyper-crosslinked polymers (HCPs) and conjugated microporous polymers (CMPs), proving that our hypothesis is effective and feasible when compared to the conventional post-sulfonation method. The excellent hydrophilicity, rich content of sulfonic acid groups, high specific surface area and hierarchical pore structure make the resulting polymer an ideal adsorbent for micro-pollutants in water. The maximum adsorption capacities for Rhodamine B (RhB), Methylene Blue (MB), Tetracycline (TC) and Ciprofloxacin (CIP) are 1075 mg g⁻¹, 1020 mg g⁻¹, 826 mg g⁻¹ and 1134 mg g⁻¹, respectively. This study not only demonstrates the preparation of efficient sulfonated porous adsorbents for the efficient removal of cationic dyes and antibiotics but also illustrates an effective method for constructing high-quality functional POP materials by optimizing the swelling state of the porous structure.