General Two-Step Method for the Fabrication of Covalent-Organic Framework-Bound Open-Tubular Capillary Columns for High-Resolution Gas Chromatography Separation of Isomers

Covalent organic frameworks (COFs) are promising as stationary phases for gas chromatography (GC). The successful anchoring of COFs to the inner walls of the capillary with good uniformity is an important prerequisite to ensure the excellent separation performance of columns. However, current methods for the fabrication of COF-based capillary columns cannot always meet this requirement when faced with different COFs, which hampers the further development of COF-based GC stationary phases. Here, we show a general two-step method for the fabrication of COF-bound capillary column. The first step enables the formation of uniform amorphous polymer layer on the inner walls of capillary, while the second step allows the facile transformation of the amorphous polymer layer into a highly crystalline COF layer. COF-bound capillary columns with different framework structures were fabricated successfully by the developed two-step method. Impressively, the COF layers bound on the inner walls of these capillary columns showed good uniformity and high crystallinity. More importantly, as an example, the fabricated Tab-DHTA-bound capillary column showed good resolution (R > 1.5) and high column efficiency (700-39,663 plates m^-1) for the tested isomers of ethylbenzene, xylene, dichlorobenzene, chlorotoluene, pinene, 1,3-dichloropropene, and propylbenzene with good precision (RSD, run-to-run, n = 5) (retention time, 0.2-0.6%; peak area, 0.5-1.1%; and peak height, 0.5-1.4%). In general, the fabricated Tab-DHTA-bound capillary column exhibited better performance for the separation isomers than commercial columns DB-5 and HP-FFAP. These results indicate that the two-step method is an efficient way to fabricate the COF-bound capillary column with excellent separation performance.