Mesoporous Carbon Nitride with π-Electron-Rich Domains and Polarizable Hydroxyls Fabricated via Solution Thermal Shock for Visible-Light Photocatalysis

Carbon nitride semiconductors are competitive candidates for visible-light-responsive photocatalysts, but encounter weakened exciton dissociation arising from the elevated Coulomb force of singlet Frenkel excitons with narrowing bandgaps. We overcome this contradiction by co-infusing π-electron-rich domains and polarizable hydroxyl units into mesoporous carbon nitride, realized by solution thermal shock. The embedded delocalized π-conjugated aromatic domains derived from nonconjugated macromolecules downshift the conduction band edge and contribute to spatial separation of photogenerated electrons in the lowest unoccupied molecular orbital and holes in the highest occupied molecular orbital. Meanwhile, polarizable hydroxyls induce distinct electron flow from heptazine-based skeletons to periphery sites and enhance water adsorption as well as proton reduction capacity. Consequently, the polymeric carbon nitride delivers an enhanced hydrogen evolution rate that is 17.5 times larger than thermally treated counterparts derived from urea fabricated via conventional strategies. These results show that our strategy can infuse different functional motifs into carbon nitride and thus improve photocatalytic activity.