Fluorination of Covalent Organic Framework Reinforcing the Confinement of Pd Nanoclusters Enhances Hydrogen Peroxide Photosynthesis.

Metal-isolated clusters (MICs) physically confined on photoactive materials are of great interest in the field of photosynthesis of hydrogen peroxide (H 2 O 2 ). Despite recent important endeavors, weak confinement of MICs in the reported photocatalytic systems leads to their low catalytic activity and stability. Herein, we report a new strategy of fluorinated covalent organic frameworks (COFs) to strongly confine Pd ICs for greatly boosting the photocatalytic activity and stability of H 2 O 2 photosynthesis. Both experimental and theoretical results reveal that strong electronegative fluorine can increase the metal-support interaction and optimize the d-band center of Pd ICs, thus significantly enhancing the stability and activity of photocatalytic H 2 O 2 . An optimal TAPT-TFPA COFs@Pd ICs photocatalyst delivers a stable H 2 O 2 yield rate of 2143 μmol h -1 g -1 . Most importantly, the as-made TAPT-TFPA COFs@Pd ICs exhibit high catalytic stability over 100 h, which is the best among the reported materials.