One-step fabrication of hydrophobic metal-organic framework@covalent organic framework hybrid as sorbent for high-performance solid-phase extraction of flavonoids

Metal-organic framework (MOF) and covalent organic framework (COF) exhibit excellent extraction performance in sample pretreatment, but their wider application is hindered by some inherent drawbacks. Herein, we successfully synthesized a novel MOF@COF hybrid material with large specific surface area, good chemical stability and reusability, which is suitable as a solid phase extraction (SPE) sorbent for the efficient extraction of flavonoids. Importantly, due to the synergistic effect, the obtained MOF@COF hybrid material showing a higher extraction efficiency than individual MOF and COF. This is mainly due to the obtained MOF@COF hybrid material combines the high specific surface area of MOF and multiple interactions (hydrophobic interaction, hydrogen bonding and π-π stacking interaction) with flavonoids conferred by the COF structure. Then, a sensitive analytical method for flavonoids with ideal linear range (1-500 ng mL-1), low detection limit (0.15-0.41 ng mL-1) and good repeatability (2.64-6.20%) was developed under optimized conditions. In addition, the MOF@COF hybrid sorbent has better selectivity for hydrophobic targets containing multiple hydrogen bond acceptors/donors. Finally, the established method was applied to the determination of flavonoids in different food samples, and satisfactory recoveries (81.4-102.1%) were obtained, which initially confirmed its applicability.