Construction of MOF@COF-derived composites for ratiometric fluorescence detection of water with ultralow background

A ratiometric sensor with ultralow background is highly desired due to its low environmental influence and high sensitivity. Herein, inspired by the solubility difference of carboxylate in aqueous and organic solvents, we prepared a core-shell structure porous zirconia-covalent organic framework (COF) composite through thermal hydrolysis of UiO-66-COF precursors in organic alkali solution. The ligand 2-aminoterephthalic acids (H₂BDC-NH₂) of UiO-66 were transformed into 2-aminoterephthalate salts (ATA salts) that existed in zirconium-oxo clusters building units. The composites emitted only yellow emission (597 nm) from the COF in organic solvent due to the insolubility of ATA salts that induce aggregation-caused quenching (ACQ) and the protection of the COF shell. Contrarily, when water was added into mixture, the ATA salts were released into solution and its fluorescence recovered at 446 nm, while the fluorescence of COF was quenched due to the blockage of the intramolecular charge transfer (ICT) process by water. Thus, a high-sensitivity ratiometric fluorescence method is obtained with ultralow background signal and fast response (less than 1 min) for sensing water in organic solvent. We believe that the proposed ratiometric fluorescence sensor based on the zirconia-COF composite will provide the guidance for detection with wide applications.