Sulfonate-Bonded Conjugated Microporous Polymer Hollowed-Out Spheres to Capture Fluoroquinolone Antibiotics and Cationic Dyes from Wastewater

Developing adsorbent materials for the efficient removal of multiple organic pollutants in water is of importance technological significance. In the present work, a kind of conjugated microporous polymer (CMP) with a hollow sphere structure was constructed by applying SiO₂ nanoparticles as a template and 1,3,5-triethynylbenzene (TEB) and 2,7-dibromocarbazole (27-DBCZ) as building blocks via the Sonogashira-Hagihara cross-coupling reaction. In order to further improve the dispersibility of the as-resulting CMPs in water, hydrophilic CMPs (H-S-CMPs) were obtained by a sulfonation modification. The adsorption performance of H-S-CMPs on dyes and antibiotics was investigated, which was based on different experimental parameters such as the initial concentration, contact time, temperature, pH, and adsorbent dose. The adsorption isotherm, kinetics, and thermodynamics were also studied, and the possible adsorption mechanism of H-S-CMPs was discussed. The experimental results illustrated that the adsorption process of H-S-CMPs on dyes and antibiotics is more consistent with the Langmuir isotherm model and the pseudo-second-order kinetic model. The maximum adsorption capacities of H-S-CMPs for rhodamine B (RhB), methylene blue (MB), ciprofloxacin, and norfloxacin were 206.2, 324.7, 222.2, and 216.9 mg/g, respectively, which were determined according to the Langmuir isothern model. In addition, the adsorption mechanism of H-S-CMPs may be attributed to the synergistic effects of hydrogen bonding, electrostatic attraction, π-π stacking, and pore filling. After 5 cycles, H-S-CMPs still maintained good stability, and their removal rate of dyes could reach more than 70%. Notably, this polymeric hollow microsphere has been less extensively investigated as an adsorbent for the removal of dyes and antibiotics. As a result, based on the designable flexibility of CMPs and the unique structure of hollow microspheres, the material holds great promise for wastewater treatment in the presence of multiple pollutants.