MOF-on-MOF-derived Fe[sbnd]Zr bimetal oxides supported on hierarchically porous carbonized wood to promote photo-Fenton degradation of ciprofloxacin

Abstract

MOF-on-MOF derivatives have served as promising heterogeneous Photo-Fenton (hetero-PF) catalysts, but its self-aggregation instability and limited photocatalytic activity inhibit the effective ciprofloxacin (CIP) removal. In this study, a novel hetero-PF catalyst, dual MOF-derived FeZr bimetal oxide embedded in a wood-converted porous carbon skeleton (ZrO2@Fe3O4/WPC), was successfully synthesized via a straightforward in-situ growth strategy combined with co-pyrolysis. The as-prepared hybrid photocatalysts, featuring a large surface area, effective porous structures, efficient light absorption and a narrow band gap demonstrated superior photo-Fenton activity, accomplishing approximately 99.1 % degradation of CIP within 120 min under neutral conditions. Furthermore, the ZrO2@Fe3O4/WPC hetero-PF system showed satisfactory performance in treating real water matrices. It can be inferred that the abundant heterojunctions, resulting from the synergistic effect of FeZr mixed oxide and the porous carbonized wood substrate, contributed to the rapid separation and migration of photogenerated electron-hole pairs. Meanwhile, the FeZr site in the graphitized carbon framework activates H2O2 to accelerate the generation of the OH and O2− radicals, leading to a heightened degradation efficiency of CIP. Besides, the photodegradation pathway of CIP is obtained by liquid chromatography-mass spectrometry (LC-MS). This study indicates that combining porous carbonized wood and heterometallic MOF derived materials provides a promising method for realizing high-efficiency photo-Fenton degradation of antibiotic water pollutions.