S,N-rich luminous covalent organic frameworks for Hg2+ detection and removal

Abstract

The challenge for simultaneous detection and removal of Hg²⁺ is the design of bifunctional materials bearing abundant accessible chelating sites with high affinity. Covalent-organic frameworks (COFs) are attracting more and more attention as potential bifunctional materials for Hg²⁺ detection due to their large specific surface area, ordered pores, and abundant chelating sites. Here, a new luminous S,N-rich COF_BTT-AMPD based on hydrophilic block unit of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (AMPD) was constructed, which improved the solubility and affinity for Hg²⁺ greatly. Another S-rich fused-ring unit of benzotrithiophene tricarbalaldehyde (BTT) enhanced the conjugation of COF_BTT-AMPD, and the methyl-rich chains block unit of AMPD effectively suppressed the aggregation-caused quenching. Thus, the COF_BTT-AMPD emitted strong fluorescence at 546 nm in liquid and solid as well as different solvent with a wide pH range, which was used for the visual detection and removal of Hg²⁺ (detection limit: 2.6 nM, linear range: 8.6 × 10^-3-20 μM, monolayer adsorption capacity: 476.19 mg g^-1) successfully. COF_BTT-AMPD-based fabric and light-emitting diode coatings were further constructed to realize the visual detection of Hg²⁺ vapor. The results reveal the potential of S,N-rich luminous COF_BTT-AMPD for Hg²⁺ detection and remediation in the environment.

Keywords: 2,2′-Azobis(2-methylpropionamidine) dihydrochloride; Benzotrithiophene tricarbalaldehyde; Covalent-organic frameworks; Fluorescence detection; Mercury ions; Removal.