Construction of Donor–Acceptor Heteroporous Covalent Organic Frameworks as Photoregulated Oxidase-like Nanozymes for Sensing Signal Amplification

Nanomaterials with enzyme-like characteristics (called nanozymes) show their extreme potentials as alternatives to natural enzymes. Covalent organic frameworks (COFs) as metal-free nanozymes have attracted huge attention for catalytic applications due to their flexible molecular design and synthetic strategies and conjugated, porous, and chemically stable architectures. Designing high-performance two-dimensional (2D) porous COF materials embedded with functional building units for modulating nanozymes’ catalytic activity is of immense importance in contemporary research. The proper combination of donor–acceptor (D–A) fragments within a porous COF skeleton is an effective strategy to decrease the band gap and provide a strong charge-transfer pathway for highly effective charge separation. Herein, two donor–acceptor heteroporous COFs using an electron-deficient 4,4′-(thiazolo[5,4-d]thiazole-2,5-diyl)dibenzaldehyde (Tz) unit or 4,4′-(benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzaldehyde (Td) unit and electron-rich tetrakis(4-aminophenyl)ethane (ETTA) linkers were presented. The resulting crystalline and heteroporous COFs showed outstanding oxidase-like activity under light irradiation, which can catalyze the oxidation of typical substrates and corresponding evolution in color and absorption. The light-activatable ETTA-Tz COF with prominent oxidase-like activity can serve as a colorimetric probe for quantitative detection of sulfide ions with a linear range of 1–50 μM and a detection limit of 0.27 μM within 3 min. The colorimetric approach could also be used for sulfide ion detection in human serum samples. The research demonstrated the future potential of D–A motifs within fully conjugated COFs to obtain excellent mimic enzyme activity.