Core-shell metal-organic framework/silica hybrid with tunable shell structure as stationary phase for high performance liquid chromatography.

Metal-organic framework/silica composite (SSU) were prepared by growing UiO-66 on the amino-functionalized SiO core-shell spheres (SiO@dSiO) via a simple one-pot synthesis approach. By controlling the concentration of Zr, the obtained SSU have two different morphologies: spheres-on-sphere and layer-on-sphere. The spheres-on-sphere structure is formed by the aggregation of UiO-66 nanocrystals on the surface of SiO@dSiO spheres. SSU-5 and SSU-20, which contain spheres-on-sphere composites have mesopores with a pore size of about 45 nm in addition to the characteristic micropores of UiO-66 with a pore size of 1 nm. In addition, UiO-66 nanocrystals were grown both inside and outside the pores of SiO@dSiO, resulting in a 27% loading of UiO-66 in the SSU. The layer-on-sphere is the surface of SiO@dSiO covered with a layer of UiO-66 nanocrystals. SSU with this structure has only a characteristic pore size of about 1 nm belonging to UiO-66 and is therefore not suitable as a packed stationary phase for high performance liquid chromatography. The SSU spheres were packed into columns and tested for the separation of xylene isomers, aromatics, biomolecules, acidic and basic analytes. With both micropores and mesopores, SSU with spheres-on-sphere structure achieved baseline separation of both small and large molecules. Efficiencies up to 48,150, 50,452 and 41,318 plates m   were achieved for m-xylene, p-xylene and o-xylene, respectively. The relative standard deviations of the retention times of anilines for run-to-run, day-to-day and column-to-column were all less than 6.1%. The results show that the SSU with spheres-on-sphere structure has great potential for high performance chromatographic separation.