Ultrafast and nanomolar level detection of H2S in aqueous medium using a functionalized UiO-66 metal–organic framework based fluorescent chemosensor

Abstract

Here, we present a 4-nitrophenyl functionalized Zr-UiO-66 MOF (MOF = metal–organic framework) and its applications towards the selective, sensitive and rapid detection of H₂S both in the aqueous medium and vapour phase. The MOF material was synthesized using the 2-(nitrophenoxy)terepththalic acid (H₂BDC-O-Ph-NO₂) linker and ZrCl₄ salt in the presence of a benzoic acid modulator. It was carefully characterized by thermogravimetric analysis (TGA), elemental analysis, powder X-ray diffraction (PXRD), FT-IR spectroscopy and surface area analysis. Noticeable thermal stability up to a temperature of 390 °C under air and the considerable chemical stability in different liquid media (H₂O, 1 M HCl, glacial acetic acid, NaOH in the pH = 8 to 10 range) confirmed the robustness of the MOF. The BET surface area (1040 m² g⁻¹) indicated the porous nature of the MOF. Remarkable selectivity of the MOF towards H₂S over other potential congeners of H₂S was observed in the aqueous medium. A very high fluorescence increment (∼77 fold) was observed after adding an aqueous Na₂S solution to the MOF suspension. The MOF probe displayed the lowest limit of detection (12.58 nM) among the existing MOF-based chemosensors of H₂S. Furthermore, it exhibited a very quick (60 s) response towards H₂S detection. The MOF compound could also detect H₂S in the vapour phase as well as in real water samples. Furthermore, we developed inexpensive MOF-coated paper strips for the naked-eye sensing of H₂S. A thorough investigation was carried out in order to elucidate the fluorescence turn-on sensing mechanism.