Synchronous Construction of Hierarchical Porosity and Thiol Functionalization in COFs for Selective Extraction of Cationic Dyes in Water Samples

Pore size and functionalization are two critical factors for covalent organic frameworks (COFs) as effective adsorbents. However, due to the low crystallinity of COFs, it is a grand challenge to accomplish pore diameter adjustment and functionalization at the same time. In this work, we developed a simple and ingenious strategy, cutting off linkage, to synchronously construct hierarchical porosity and modify thiol groups in COFs under mild conditions. The hybrid COFs containing disulfide bonds were designed and synthesized, and then the disulfide bonds were cleaved by glutathione, resulting in the formation of thiol groups as well as the increase in pore size caused by skeleton defects. The pore diameter of thiol-functionalized hierarchical porous COFs (denoted as HP-TpEDA-SH) was concentrated at 2.6 and 3.5 nm. Thanks to the electrostatic attraction of thiol groups to cationic dyes and the higher number of available adsorption sites, the maximum extraction amounts of methylene blue (MB), malachite green (MG), and crystal violet (CV) by HP-TpEDA-SH were 2.6, 2.1, and 3.3 times those of microporous COFs under optimal extraction conditions, respectively. The proposed analytical method (solid-phase extraction-high-performance liquid chromatography/ultraviolet (SPE-HPLC/UV)) with HP-TpEDA-SH as the adsorbent showed low detection limits of 1.3, 0.13, and 0.12 μg·L–1 for MB, MG, and CV, respectively. The recoveries of three spiked water samples ranged from 81.5 to 113.8%, with relative standard deviations (RSDs) less than 9.7%. This work not only opened a new avenue for the preparation of functionalized hierarchical porous COFs but also established an effective method for detecting trace cationic dyes in fishery water.