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

Yuanyuan Yin; Jian Zhang; Chengshan Ji; He Tao; Yulin Yang

doi:10.1016/j.jcis.2024.03.042

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

J Colloid Interface Sci. 2024 Jun 15:664:551-560. doi: 10.1016/j.jcis.2024.03.042. Epub 2024 Mar 7.

Authors

Yuanyuan Yin¹, Jian Zhang², Chengshan Ji¹, He Tao¹, Yulin Yang³

Affiliations

¹ MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, PR China.
² MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, PR China. Electronic address: zhaji@hit.edu.cn.
³ MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, PR China. Electronic address: ylyang@hit.edu.cn.

PMID: 38484524
DOI: 10.1016/j.jcis.2024.03.042

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 (q_max = 210.6 mg∙g^-1), NFZ (q_max = 111.5 mg∙g^-1) and NFT (q_max = 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.

Keywords: Adsorption; Copper(I)-iodide cluster; Fluorescence; Metal-organic frameworks; Water treatment.