Natural phenol-inspired porous polymers for efficient removal of tetracycline: Experimental and engineering analysis

Efficient and feasible removal of trace antibiotics from wastewater is extremely important due to its environmental persistence, bioaccumulation, and toxicity, but still remains a huge challenge. Herein, three natural phenol-inspired porous organic polymers were fabricated from natural phenolic-derived monomers (p-hydroxy benzaldehyde, 2,4-dihydroxy benzaldehyde and 2,4,6-trihydroxy benzaldehyde) and melamine via polycondensation reaction. Characterization highlighted that the increasing contents of hydroxyl groups in monomers induced an increase of the polymer total porosity and promoted the formation of a highly microporous structure. With mesopore-dominated pore (average pore diameter 9.6 nm) and large pore volume (1.78 cm³/g), p-hydroxy benzaldehyde-based porous polymer (1-HBPP) exhibited ultra-high maximum adsorption capacity (q_max) of 697.6 mg/g for tetracycline (TC) antibiotic. Meanwhile, the porous networks and plentiful active sites of 1-HBPP enabled fast adsorption kinetics (within 10 min) for TC removal, which could be well described by the pseudo-second-order model. Dynamic adsorption studies showed that 1-HBPP could be used in fixed-bed adsorption column (FBAC) with high removal efficiency (breakthrough volume per unit mass, 13.2 L/g) and dynamic adsorption capacity (201.6 mg/g), which were much higher than other reported adsorbents. The breakthrough curves both well matched with Thomas and Yoon-Nelson models in FBAC treatment. Moreover, removal mechanism analysis affirmed that pore-filling, hydrogen bonding, electrostatic interactions and π-π stacking interactions were main driving forces for TC adsorption. The prepared natural phenol-inspired porous adsorbents show great potential in antibiotics removal from wastewater, and this strategy would promote the sustainable and high-value utilization of natural phenolic compounds.