Amine/hydrazone functionalized Cd(II)/Zn(II) metal-organic framework for ultrafast sensitive detection of hazardous 2,4,6-trinitrophenol in water.

Amine/hydrazone functionalized dual ligand Cd(II)/Zn(II) based metal-organic frameworks (MOFs) denoted as CdMOF- and ZnMOF-NH, respectively were synthesized via a simple conventional high-yield reflux method using low-cost and readily available starting materials, i.e., a Schiff base linker, 4-pyridylcarboxaldehydeisonicotinoylhydrazone (L) and 2-aminoterephthalic acid (Hata) linker. Crystallographic and thermogravimetric studies confirmed the formation of MOFs with good crystallinity and thermal stability. Photoluminescence studies point out that both MOFs can be used efficiently for fast sensing of 2,4,6-trinitrophenol (TNP) in water with noticeable turn-off quenching response. Their limits of detection (LODs) for TNP were 7 ppb and 10 ppb, respectively with enhanced selectivity toward TNP (over other nitro explosives) as verified by competitive nitro explosive tests. Density functional theory calculations and spectral overlap were used to assess the sensing mechanism. These MOF-based fluorescent sensing systems for TNP are demonstrated to have easy recoverability and high sensitivity.