Picolinamide Functionalization on Carbon Nitride Edges for Enhanced Charge Separation and Photocatalytic Hydrogen Evolution.

The periodical distribution of N and C atoms in carbon nitride (CN) not only results in localized electrons in each tri-s-triazine unit, but oxidation and reduction sites are in close contact spatially, resulting in severe carrier recombination. Herein, the hydrothermal method was first employed to synthesize carbon nitride (HCN), and then picolinamide (Pic) molecules were introduced at the edge of the carbon nitride so that the photo-generated electrons of the whole structure of the carbon nitride system were transferred from the center to the edge, which effectively promoted the separation of photo-generated carriers and inhibited the recombination of carriers in the structure. The introduced picolinamide not only changed the π-conjugated structure of the entire system but also acted as an electron-withdrawing group to promote charge transfer. The photocatalytic hydrogen evolution rate (HER) of the optimized HCN-Pic-1:1 sample could reach 918.03 μmolg h, which was 11.8 times higher than that of the HCN, and the performance also improved.