Enzyme-Click Postsynthetic Modification of Covalent Organic Frameworks for Photocatalytic H₂O₂ Production

Area of Science:

• Materials Science
• Organic Chemistry
• Biocatalysis

Background:

• Postsynthetic modification (PSM) is crucial for tailoring covalent organic frameworks (COFs).
• Enzymatic catalysis offers mild, efficient, and eco-friendly reaction conditions.

Purpose of the Study:

• To develop a novel enzymatic PSM strategy for functional group engineering in COFs.
• To investigate the impact of implanted functional groups on photocatalytic performance.

Main Methods:

• Utilized enzymatic catalysis for covalent implantation of 2-hydroxyethylthio (-S-EtOH) and ethylthio (-S-Et) groups into COFs.
• Performed theoretical calculations and in situ experiments to analyze the mechanism and performance.

Main Results:

• Achieved high grafting efficiency of -S-EtOH and -S-Et groups under ambient aqueous conditions.
• Demonstrated that -S-EtOH incorporation enhances exciton dissociation and charge separation.
• -S-EtOH facilitated proton supply and lowered Gibbs free energy for photocatalytic H2O2 production.

Conclusions:

• Established a novel enzymatic PSM strategy for COF functionalization.
• Highlighted the potential of combining enzymatic catalysis with reticular materials engineering.
• Showcased improved photocatalytic H2O2 production through tailored COF functionalization.