Diamino group-functionalized Zr-based metal-organic framework for fluorescence sensing of free chlorine in the aqueous phase and Knoevenagel condensation.

We developed a porous diamino group-functionalized Zr(IV) metal-organic framework (MOF). The synthesized MOF has a similar structure to DUT-52 (DUT = Dresden University of Technology), which has a face-centered cubic structure with an 3̄ space group. The synthesized material (DUT-52-(NH2)2-1) was solvent exchanged with methanol (MeOH) and activated at 100 °C overnight. Both the as-synthesized and activated materials (DUT-52-(NH2)2-1') are thermally stable until 300 °C. The Brunauer-Emmett-Teller (BET) surface area of DUT-52-(NH2)2-1' was found to be 413 m g. DUT-52-(NH2)2-1' showed a significant quenching of fluorescence response after coming in contact with free chlorine (ClO) in an aqueous medium. The selectivity of DUT-52-(NH2)2-1' towards ClO was not significantly hampered in the presence of any competitive ion. The limit of detection (LOD) value was found to be 0.08 μM in phosphate-buffered saline (PBS, pH = 7.4). DUT-52-(NH2)2-1' is recyclable and very sensitive towards ClO. Moreover, the paper strip method was developed for onsite identification of ClO. Furthermore, the catalytic activity of DUT-52-(NH2)2-1' was tested in the Knoevenagel condensation between benzaldehyde and cyanoacetamide. The experimental results clearly indicate that DUT-52-(NH2)2-1' exhibits high activity with very high selectivity towards condensation products. The solid was reusable three times with no decay in its activity, as evidenced by powder X-ray diffraction (PXRD), field emission scanning electron microscopy (FE-SEM) and fourier transform infrared (FT-IR).