Rare [Cu4I2]2+ cationic cluster-based metal-organic framework and hierarchical porous composites design for effective detection and removal of roxarsone and antibiotics

Abstract

Fluorescence quenching induced by photoinduced electron transfer (PET) stands as an effective strategy for identifying water pollutants. Herein, a novel (4, 8)-connected three-dimensional framework Cu(I)-MOF ([Cu2I(tpt)]n) with unique 8-connected [Cu4I2]2+ cationic clusters is designed by employing the nitrogen-rich ligand (Htpt = 5-[4(1H-1,2,4-triazol-1-yl)]phenyl-2H-tetrazole). Water-stabilized Cu(I)-MOF exhibits outstanding fluorescence properties, facilitating its application in detecting organic pollutants in water. Benefiting from the fact that the Cu(I)-MOF possesses a higher lowest unoccupied molecular orbitals (LUMO) energy level than that of the analyte, the rapid d-PET can occur, entitling Cu(I)-MOF to a sensitive fluorescence quenching response to roxarsone (ROX), nitrofurazone (NFZ) and nitrofurantoin (NFT) (with detection limits as low as 0.13 µM, 0.15 µM, and 0.13 µM, respectively). The nitrogen-containing sites of melamine foam (MF) are utilized to facilitate the anchoring and growth of Cu-MOF crystals, which enables the preparation of hierarchical microporous − macroporous Cu(I)-MOF/MF composites. The ordered porous structure of Cu(I)-MOF/MF provides cavities and open sites for the efficient removal of ROX (qmax = 210.6 mg∙g−1), NFZ (qmax = 111.5 mg∙g−1) and NFT (qmax = 238.9 mg∙g−1) from water. This characteristic endows the Cu(I)-MOF/MF with rapid and recyclable adsorption capacity. Therefore, this work provides valuable insights to address the problem of detection and removal of pollutants in the aquatic environment.