In situ growth of COF-rLZU1 on the surface of silica sphere as stationary phase for high performance liquid chromatography

Abstract

The composite materials consist of Covalent Organic Frameworks (COFs) and silica have been regarded as a kind of promising stationary phases due to combination of the large specific surface area and good mechanical strength of porous silica microspheres and the porous structure and the excellent stability of COFs. Herein, a novel COFs-silica composite (SiO2@rLZU1, reduced Lan Zhou University-1) was prepared via an in-situ growth strategy with a 32 nm-thick COFs layer on the surface of silica and a 2.2 nm-thick COFs layer on the inner surface of the mesopores of spherical silica (5 μm, 120 Å). With secondary amine and phenyl groups, the novel stationary phase provided hydrophilic, hydrophobic and π-π interactions when used in HPLC, showing different selectivity from typical reversed-phase stationary phases. Probe molecules with aromatic moieties varying in polarity, including acidic (phenol, pyrocatechol, and pyrogallol), basic (aniline, 4-chloroaniline, and 4-nitroaniline) and neutral (benzene homologues) compounds, were all baseline separated on the SiO2@rLZU1 column, indicating its excellent separation performance. Besides, the SiO2@rLZU1 column also exhibited great repeatability with intraday RSDs of the retention time of three anilines less than 0.31% (n = 6) and peak area less than 1.63% (n = 6). On the SiO2@rLZU1 column, satisfied results were achieved in the separation of real samples such as fullerenes and coking wastewater, suggesting the great potential of the as-synthesized stationary phase in HPLC applications.