Wettability tunable metal organic framework functionalized high internal phase emulsion porous monoliths for fast solid-phase extraction and sensitive analysis of hydrophilic heterocyclic amines.

Surface wettability greatly influences the adsorptive, catalytic, and diffuse performances of a porous material. To realize the improved adsorption performance to hydrophilic heterocyclic amines (HAs), polymeric high internal phase emulsions (polyHIPEs) that can be tuned from hydrophobic to hydrophilic is synthesized by facilely regulating the amount of metal organic frameworks (MOFs). The water contact angle of the MOFs and polyHIPEs hybrids (MOFs@polyHIPEs) decreases from 133° to 0° as the amount of amide-modified MOFs increases from 0% to 10%. The hydrophilization of divinybenzene (DVB) based polyHIPEs by MOFs hybridization significantly enhances their adsorption performance and enables them to be suitable for the solid phase extraction (SPE) of hydrophilic HAs. Under the optimized conditions, the MOFs@polyHIPEs achieve adsorption capacities ranging from 42.89 to 86.71 µg/g for HAs through the π-π interaction and hydrogen bonding. The adsorption follows the pseudo-second-order kinetic model, and the nitrogen atoms in/on the imidazole ring are identified as the active adsorption sites for hydrogen bonding. This SPE method, along with HPLC-MS detection, provides detection limits of HAs as low as 0.00020-0.00040 ng/mL. This work offers a feasible strategy in tuning the surface wettability of polyHIPEs without post-modification to achieve high-efficiency enrichment and analysis of HAs.