A mussel-pearl side chain interaction in mercury(II) and phenol removal by sulfur-functionalized covalent organic frameworks: A DFT study.

The covalent organic framework materials (COFs) with excellent chemical and physical characteristics have been rapidly developed as adsorbents in the application of environmental remediation. In the design of COFs, the selection of functional groups and side chains is of great significance. Herein, density function theory (DFT) method is used to illustrate the adsorption behavior and mechanism of three sulfur-functionalized COFs (S-COFs) for the adsorption of mercury(II) and phenol. According to the analysis of geometric configurations and electronic properties, it demonstrated that the side chains of S-COFs with high flexibility and concentrated sulfur-functional groups, acting like a closed mussel which tightly confined the contaminants, the highest adsorption was -24.32 kcal/mol. The adsorption mechanism of phenol and mercury(II) on S-COFs was elucidated. For phenol, hydrogen bonds and π-π stacking interaction played an important role in the adsorption process, while the coordination interaction was dominated for the adsorption of mercury(II). This research explains the importance of selecting appropriate functional groups and side chains for COFs in the removal of contaminants in the molecular scale, and reveals the great potential of COFs in environmental remediation applications.