High-Efficiency and Versatile Approach To Fabricate Diverse Metal–Organic Framework Coatings on a Support Surface as Stationary Phases for Electrochromatographic Separation

A large number of metal–organic frameworks (MOFs) have exhibited increasingly wide utilization in the field of chromatographic separation owing to their intrinsic fascinating properties. However, the previous studies on supported MOF coating-based chromatographic separation focused only on the synthesis and chromatographic performance of a certain kind of supported MOF coatings as stationary phases using the multiple-step, complicated, and time-consuming modification methods, which severely impeded the widespread application of MOFs in separation science. Herein, a high-efficiency and versatile methodology toward diverse supported MOF coating-based stationary phases to achieve high-efficiency chromatographic separation was first reported based on the immobilized cysteine (Cys)-triggered in situ growth (ICISG) strategy. As a proof-of-concept demonstration, four types of MOF crystals consisting of different ligands and metal ions (Zn2+, Cu2+, Fe3+, and Zr4+) were conveniently and firmly grown on a Cys-modified capillary using the ICISG strategy and employed as the functional stationary phase for electrochromatographic separation. A broad variety of neutral, acidic, and basic compounds were all separated in a highly efficient manner on the developed four MOF-coated columns. The maximum theoretical plate number for Cys-MIL-100­(Fe)@capillary was close to 1.0 × 105 plates/m, and the intraday, interday, and column-to-column repeatabilities of retention times for the four MOF-modified columns were all less than 5.25%. More interestingly, the diversified separation performance of the developed MOF-coated columns indicated that the preparation strategy and the skeletal structure of the MOF coating-based stationary phases have a significant influence on the electrochromatographic separation performance and column capacity. Benefiting from the strong universality and high applicability of the developed ICISG strategy, the present study provides an effective route to facilitate the design and fabrication of novel functional MOF-based chromatographic stationary phases.