Core-shell MOFs-based composites of defect-functionalized for mixed-mode chromatographic separation.

• A functionalized MOFs-based composite with dispersed hierarchical pores was fabricated. • It was applied as mixed-mode stationary phase for fast and efficient separation. • It exhibited superior selectivity for separation of various analytes. • It highlighted the role of the defect of MOFs and function of L-Cysteine. The micropores of the metal-organic frameworks (MOFs) endow with the advantages of size selectivity and large specific surface area, etc., but they limit their applications toward the control of diffusion and transport processes. Here, we report a strategy to prepare the hierarchical porous material, functional defect, which allows incorporation of L-Cysteine in the MOF by defect-loading. Silica microspheres were modified with these materials to form core-shell composites and used as mixed-mode stationary phases for chromatographic separations. Compared with the traditional MOFs-based stationary phase, it exhibited superior efficiency and selectivity for separation of various analytes and highlighted the role of defect of MOFs and function of L-Cysteine. In addition to the rapid separation of hydrophobic compounds, the stationary phase showed great potential in the separation of hydrophilic analytes, especially for separation of ten carbohydrates and eight sulfonamides. It showed excellent chromatographic reproducibility and stability, and the repeatability of preparation was investigated by relative standard deviations of retention time and/or column efficiency of objective compounds, which was among different batches less than 1.81%. This demonstration provided deep understanding of separation mechanism between MOF-based composites with functional defect and analytes, and stimulated the wide applications of such defective MOFs complexes in separations and analysis. [ABSTRACT FROM AUTHOR]