José Patricio Peña-Jaramillo

Ciprofloxacin (CIP) is a persistent fluoroquinolone antibiotic frequently detected in water bodies, and its efficient mineralization remains a challenge in wastewater treatment. In this work, iron oxide–chitosan macroporous nanocomposite hydrogels were developed as heterogeneous catalysts for the electro-Fenton degradation of CIP. The materials were synthesized via Pickering high internal phase emulsion templating, yielding monoliths with a three-dimensional interconnected porous structure, an average pore size of 18.9 ± 0.7 µm, a window size of 8.1 ± 0.7 µm, an openness degree of 39.6%, a specific surface area of 1.77 m² g⁻¹, an iron content of 64.2 mg g⁻¹, and a crosslinking degree of 92.1%. The monoliths exhibited controlled swelling in aqueous medium at pH 3, with a gravimetric water uptake of 142.1 ± 2.3% and a volumetric swelling of 39.3 ± 1.2% at equilibrium. Iron oxide particles remained exposed on the porous surface, providing accessible catalytic sites, while the interconnected porosity favored reactant diffusion. Compared with direct anodic oxidation, which achieved 32% total organic carbon removal after 20 min, the heterogeneous electro-Fenton process using the synthesized monoliths as catalysts showed superior performance, reaching nearly 95% removal within 2 min and complete mineralization within 15 min. This enhanced performance was associated with higher hydroxyl radical generation (~3.5 µM) than that observed for anodic oxidation alone (~1.5 µM). These findings highlight the potential of biodegradable iron oxide–chitosan macroporous hydrogels as sustainable catalysts for antibiotic removal from water.