A new nano-scale spherical vinyl-functionalized covalent organic polymer (TAPT-DVA-COP) with uniform sizes around 300 nm was initially constructed using 2,5-divinyl-1,4-benzaldehyde (DVA) and 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) as monomers. Then, a sulfonic acid (-SO₃H) modified COP termed COP-SO₃H was developed based on post-sythesis method employing TAPT-DVA-COP as precursor. Capillary electrochromatography (CEC) monolithic columns were fabricated using the physical doping technique to exhibit the application potential of TAPT-DVA-COP and COP-SO₃H. Compared to the TAPT-DVA-COP monolithic column, the COP-SO₃H monolithic column achieved a highly selective separation between analytes with different properties, including monosubstituted benzenes, alkylbenzenes, hydroxybenzoates, nucleoside bases, and biogenic amines. Non-covalent interaction (NCI) analysis and experimental data show that the synergism of the sulfonic acid group and aromatic moieties on COP-SO₃H endows the new stationary phase with diverse interactions, including ion exchange, hydrophobic, π-π and hydrogen bonding. In addition, the COP-SO₃H monolithic column exhibited good reproducibility and excellent potential for the determination of hydroxybenzoates in compact powders and alkylbenzenes in effluent samples.

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