Efficient nitro-aromatic sensor via highly luminescent Zn-based metal-organic frameworks

Highly stable zinc-based luminescent metal-organic framework (LMOF) [(Zn2-(NDC)2(bpy)·Gx) where NDC-2,6-naphthalene dicarboxylic acid, bpy - 4,4' bipyridine, and G - guest solvent molecules] is synthesized via solvothermal method at different synthesizing temperatures (120, 150 and 180∘C) for the detection of nitro-aromatics. Sample structure and presence of ligands is confirmed by X-ray diffraction and FTIR measurements, respectively. The photoluminescence properties of synthesized LMOF samples show the strong emission intensity in ethanol at 376 nm when it is excited at 240 nm. The detection limit is calculated using fluorescence quenching for the various nitro-analytes (2,4-DNP, 2-Nitrotoulene, 4-Nitrophenol, and Nitrobenzene) revealed that it is least for the sample synthesized at 150∘C with the maximum percentage in fluorescence decay. The thermal stability of as-synthesized samples is analysed using thermogravimetry analysis (TGA) which reveals that sample synthesized at 150∘C is the most stable sample. The TGA analysis also shows that on further heating from 526∘C to 980∘C decomposition of zinc metal and formation of zinc oxide takes place. FE-SEM confirms the cuboidal morphology with an average particle size of 12.62 nm, corroborated by the TEM analysis. The fluorescence quenching mechanism is explained on the basis of dipole-dipole and π-stacked interactions between the MOF and nitro-aromatics that play a prominent role in the sensing of nitro-analytes. Synthesized MOF samples show excellent recyclability in fluorescence quenching even after the fourth cycle, i.e. more than 95% and is sensitive to detect nitro-aromatics even upto 0.284 µM, and the results can generalize the explosive sensor technology and sensing various nitro-based pollutants.