Ionic liquid assisted in situ growth of nano-confined ionic liquids/metal-organic frameworks nanocomposites for monolithic capillary microextraction of microcystins in environmental waters

Abstract

A facile in-situ ionothermal synthesis strategy for fabrication of ionic liquids/metal−organic frameworks (MOFs) (ILs@ZIF-8) nanocomposites hybrid monolith has been proposed to facilitate highly effective capillary microextraction (CME) of ultra-trace microcystins (MCs) in environmental waters. The ZnO nanoparticles (ZnO-NPs) were initially introduced into a precursor polymer monolith, and acted as the metal sources and anchoring seeds to construct ILs@ZIF-8 nanocomposites hybrid monolith via a nanoparticle-directed in-situ growth route in confined imidazolium ionic liquids. Detailed characterization based on scanning electron microscopy (SEM), X-ray diffraction (XRD) and N2 adsorption-desorption isotherms confirmed that both the morphology and porous structure of ZIF-8 were finely tuned by the incorporation of ILs, which acted as solvents and structure directing agent. The confinement of ILs in ZIF-8 framework endows the ILs@ZIF-8 hybrid monolith additional adsorption sites and satisfied water stability for the synergistic enhancement of adsorption efficiency of MCs via multiple interactions (including π-π stacking, hydrogen bonding, hydrophobic and electrostatic interactions). Coupling ILs@ZIF-8 hybrid monolith-based CME to LC-MS enabled an efficient and sensitive analysis of MCs in surface waters with ultra-low detection limits (LOD ≤ 1.4 ng L−1) and satisfactory recoveries (70.2%−107.0%). This study showed great potential for feasible design and fabrication of ILs@MOFs composites with synergistic and tunable structures toward efficient sample preparation applications.